Near-infrared-absorbing composition, near-infrared cut filter
obtained using same, process for producing said cut filter, camera module and process for producing same, and solid photographing element

ABSTRACT

Provided are a near-infrared-absorbing composition capable of forming a cured film having excellent heat resistance while maintaining high near-infrared-shielding properties, a near-infrared cut filter obtained using the same, a process for producing said cut filter, a camera module and a process for producing the same, and a solid photographing element. 
     The near-infrared-absorbing composition includes a near-infrared-absorbing compound (A1) obtained from a reaction between a low-molecular-weight compound which has two or more coordination sites to a metal component or a coordination site to a metal component and a cross-linking group and has a molecular weight of 1800 or lower or a salt thereof and the metal component and a near-infrared-absorbing compound (B) obtained from a reaction between a high-molecular-weight compound having a repeating unit represented by Formula (II) below or a salt thereof and a metal component. 
     In Formula (II), R 2  represents an organic group, Y 1  represents a single bond or a divalent linking group, and X 2  represents the coordination site to the metal component.

This application is a Continuation of PCT International Application No.PCT/JP2014/069481 filed on Jul. 23, 2014, which claims priority under 35U.S.C §119(a) to Japanese Patent Application No. 2013-153984 filed onJul. 24, 2013. Each of the above application(s) is hereby expresslyincorporated by reference, in its entirety, into the presentapplication.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a near-infrared-absorbing composition,a near-infrared cut filter obtained using the same, a process forproducing said cut filter, a camera module and a process for producingthe same, and a solid photographing element.

2. Description of the Related Art

A CCD or CMOS imaging sensor that is a solid photographing element forcolor images has been used for video cameras, digital still cameras,mobile phones equipped with a camera function, and the like. In thesolid photographing element, since a silicon photodiode havingsensitivity to near-infrared rays is used in the light receivingsection, it is necessary to correct the luminosity factor, and anear-infrared cut filter (hereinafter, also referred to as IR cutfilter) is frequently used.

As a material for forming the near-infrared cut filter, JP2010-134457Adiscloses an infrared-shielding film including an infrared shieldingresin formed by adding a metallic compound to a copolymer of a reactantbetween (meth)acrylamide and phosphoric acid or a hydrolysate thereofand a compound having an ethylenic unsaturated bond.

SUMMARY OF THE INVENTION

Here, as a result of studying the infrared-shielding resin disclosed byJP2010-134457A, it has been found that near-infrared-shieldingproperties are insufficient, and heat resistance is also insufficient.

The present invention intends to solve such problems, and an object ofthe present invention is to provide a cured film having excellent heatresistance while maintaining high near-infrared-shielding properties.

The present inventors found that the above-described problems can besolved by formulating a near-infrared-absorbing compound (A1) and anear-infrared-absorbing compound (B) which will be described belowand/or a near-infrared-absorbing compound (A2) described below into anear-infrared-absorbing composition.

Specifically, the problems have been solved using the following means<1>, preferably, means <2> to <18>.

<1> A near-infrared-absorbing composition including anear-infrared-absorbing compound (A1) obtained from a reaction between alow-molecular-weight compound which has two or more coordination sitesto a metal component or a coordination site to a metal component and across-linking group and has a molecular weight of 1800 or lower or asalt thereof and the metal component; and

a near-infrared-absorbing compound (B) obtained from a reaction betweena high-molecular-weight compound having a repeating unit represented byFormula (II) below or a salt thereof and a metal component:

in Formula (II), R² represents an organic group, Y¹ represents a singlebond or a divalent linking group, and X² represents the coordinationsite to the metal component.

<2> A near-infrared-absorbing composition including anear-infrared-absorbing compound obtained from a reaction between alow-molecular-weight compound which has two or more coordination sitesto a metal component or a coordination site to a metal component and across-linking group and has a molecular weight of 1800 or lower or asalt thereof, a high-molecular-weight compound having a repeating unitrepresented by Formula (II) below or a salt thereof, and a metalcomponent:

in Formula (II), R² represents an organic group, Y¹ represents a singlebond or a divalent linking group, and X² represents the coordinationsite to the metal component.

<3> The near-infrared-absorbing composition according to <1> or <2>, inwhich the low-molecular-weight compound is a compound represented byFormula (I) below:

R¹(—X¹)_(n1)   (I)

in Formula (I), R¹ represents an n1-valent group, X¹ represents thecoordination site to the metal component, and n1 represents an integerfrom 2 to 6.

<4> The near-infrared-absorbing composition according to <1> or <2>, inwhich the low-molecular-weight compound is a compound represented byFormula (a1-i) below:

R¹⁰⁰-L¹⁰⁰-(X¹⁰⁰)_(n)   (a1-i)

in Formula (a1-i), X¹⁰⁰ represents the coordination site to the metalcomponent, n represents an integer from 1 to 6, L¹⁰⁰ represents a singlebond or a linking group, and R¹⁰⁰ represents a cross-linking group.

<5> The near-infrared-absorbing composition according to any one of <1>to <4>, in which a weight-average molecular weight of thehigh-molecular-weight compound having the repeating unit represented byFormula (II) or a salt thereof is in a range of 2,000 to 2,000,000.

<6> A near-infrared-absorbing composition including anear-infrared-absorbing compound (A2) obtained from a reaction between alow-molecular-weight compound having a molecular weight of 1800 or lowerwhich is represented by Formula (III) below or a salt thereof and ametal component:

R³(—X¹)_(n2)   (III)

in Formula (III), R³ represents an n2-valent group, X¹ represents acoordination site to the metal component, and n2 represents an integerfrom 3 to 6.

<7> The near-infrared-absorbing composition according to any one of <1>to <6>, in which the metal component is a copper component.

<8> The near-infrared-absorbing composition according to any one of <1>to <7>, in which the coordination site to the metal component is an acidgroup.

<9> The near-infrared-absorbing composition according to any one of <1>to <5>, including a near-infrared-absorbing compound (C) having apartial structure represented by Formula (IV) below:

in Formula (IV), R⁴ represents an organic group, R⁵ represents adivalent group, Y² represents a single bond or a divalent linking group,each of X³ and X⁴ independently represents a site at which a coordinatebond is formed with copper, and Cu represents a copper ion.

<10> The near-infrared-absorbing composition according to <9>, in whichthe site at which a coordinate bond is formed with copper is an acidgroup ion site derived from an acid group.

<11> The near-infrared-absorbing composition according to any one of <1>to <10>, in which a content of copper in the near-infrared-absorbingcomposition is in a range of 2% by mass to 50% by mass of a total amountof solid contents in the near-infrared-absorbing composition.

<12> The near-infrared-absorbing composition according to any one of <1>to <11>, further including an organic solvent.

<13> A near-infrared cut filter obtained using thenear-infrared-absorbing composition according to any one of <1> to <12>.

<14> The near-infrared cut filter according to <13>, in which apercentage of a change in absorbance at a wavelength of 400 nm and apercentage of a change in absorbance at a wavelength of 800 nm beforeand after heating of the near-infrared cut filter at 200° C. for fiveminutes are both 7% or lower.

<15> A process for producing a near-infrared cut filter including a stepof forming a near-infrared cut filter by applying thenear-infrared-absorbing composition according to any one of <1> to <12>to a light-receiving side of a solid photographing element.

<16> A solid photographing element including a near-infrared cut filterobtained using the near-infrared-absorbing composition according to anyone of <1> to <12>.

<17> A camera module including a solid photographing element; and anear-infrared cut filter disposed on a light-receiving side of the solidphotographing element, in which the near-infrared cut filter accordingto <14> is used.

<18> A process for producing a camera module including a solidphotographing element; and a near-infrared cut filter disposed on alight-receiving side of the solid photographing element, including astep of forming a near-infrared cut filter by applying thenear-infrared-absorbing composition according to any one of <1> to <12>to the light-receiving side of the solid photographing element.

According to the present invention, it has become possible to provide acured film having excellent heat resistance while maintaining highnear-infrared-shielding properties.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is an imaginary view illustrating an example of anear-infrared-absorbing compound in the present invention.

FIG. 2 is an imaginary view illustrating another example of thenear-infrared-absorbing compound in the present invention.

FIG. 3 is a schematic sectional view illustrating a constitution of acamera module including a solid photographing element according to anembodiment of the present invention.

FIG. 4 is a schematic sectional view of the solid photographing elementaccording to the embodiment of the present invention.

FIG. 5 is a schematic sectional view illustrating an example of aperiphery of a near-infrared cut filter in the camera module.

FIG. 6 is a schematic sectional view illustrating an example of theperiphery of the near-infrared cut filter in the camera module.

FIG. 7 is a schematic sectional view illustrating an example of theperiphery of the near-infrared cut filter in the camera module.

FIG. 8 is an imaginary view illustrating an example of thenear-infrared-absorbing compound.

FIG. 9 is an imaginary view illustrating an example of thenear-infrared-absorbing compound.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

Hereinafter, the contents of the present invention will be described indetail.

In the present specification, “to” used to express numerical ranges willbe used with a meaning that numerical values before and after the “to”are included in the numerical ranges as the lower limit value and theupper limit value.

In the present specification, “(meth)acrylates” represent acrylates andmethacrylates, “(meth)acrylic” represents acrylic and methacrylic, and“(meth)acryloyl” represents acryloyl and methacryloyl.

In the present specification, “monomers” and “monomers” refer to thesame thing. In addition, “polymers” and “polymers” refer to the samething.

In the present specification, regarding the denoting of a group (atomicgroup), a group not denoted with ‘substituted’ or ‘unsubstituted’ refersto both a group (atomic group) having no substituents and a group(atomic group) having a substituent.

A near-infrared ray in the present invention refers to a ray having amaximum absorption wavelength in a range of 700 nm to 2500 nm andparticularly in a range of 700 nm to 1000 nm.

A near-infrared-absorbing property in the present invention refers to aproperty of having the maximum absorption wavelength in thenear-infrared range.

The main chain of a polymer in the present invention refers to an atomor an atomic group required to form a skeleton (long chain) of thepolymer, and, in a case in which part or all of the skeleton is a cyclicgroup (for example, an aryl group), the cyclic group is also a part ofthe main chain. In addition, an atom directly bonded to this main chainis also considered as a part of the main chain The side chain of thepolymer in the present invention refers to a portion other than the mainchain. Here, a functional group directly bonded to the main chain (forexample, an acid group described below or a salt thereof) is alsoconsidered as the side chain.

Near-Infrared-Absorbing Composition

A near-infrared-absorbing composition of the present invention includesat least one of a near-infrared-absorbing compound (A1:low-molecular-weight type) obtained from a reaction between alow-molecular-weight compound which has two or more coordination sitesto a metal component or a coordination site to a metal component and across-linking group and has a molecular weight of 1800 or lower or asalt thereof and the metal component, a near-infrared-absorbing compound(B: high-molecular-weight type) obtained from a reaction between ahigh-molecular-weight compound having a repeating unit represented byFormula (II) below or a salt thereof (hereinafter, also referred to as acompound represented by Formula (II)) and a metal component, and anear-infrared-absorbing compound (A2: low-molecular-weight type)obtained from a reaction between a metal component and alow-molecular-weight compound having a molecular weight of 1800 or lowerwhich is represented by Formula (III) below or a salt thereof.

In Formula (II), R² represents an organic group, Y¹ represents a singlebond or a divalent linking group, and X² represents a coordination siteto the metal component.

The near-infrared-absorbing composition of the present invention mayinclude a near-infrared-absorbing compound obtained from a reactionbetween a metal component, the low-molecular-weight compound or a saltthereof, and a high-molecular-weight compound having a repeating unitrepresented by Formula (II) below or a salt thereof.

R³(—X¹)_(n2)   (III)

In Formula (III), R³ represents an n2-valent group, X¹ represents acoordination site to the metal component, and n2 represents an integerfrom 3 to 6.

<Near-infrared-absorbing composition including near-infrared-absorbingcompound (A1: low-molecular-weight type) and near-infrared-absorbingcompound (B: high-molecular-weight type)>

The composition of the present invention preferably includes at leastthe near-infrared-absorbing compound (A1) and thenear-infrared-absorbing compound (B).

When the near-infrared-absorbing composition of the present inventionincludes at least one of the near-infrared-absorbing compound (A1) andthe near-infrared-absorbing compound (B) and the near-infrared-absorbingcompound (A2), it is possible to form a cured film having excellent heatresistance while maintaining high near-infrared-shielding properties.While being an assumption, the reason therefor is considered as follows.

In a case in which the near-infrared-absorbing composition of thepresent invention includes at least the near-infrared-absorbing compound(A1) and the near-infrared-absorbing compound (B), in the composition,the coordination site (for example, one or more sites selected from acoordination site to be coordinated with an anion (specifically an acidgroup or a salt thereof and more specifically an acid group ion sitederived from an acid group) and a coordination site to be coordinatedwith an unshared electron pair) to the metal component in the compoundrepresented by Formula (II) and a metal ion in the metal component(preferably a copper ion) are bonded to each other (for example, acoordinate bond). Furthermore, the metal ion bonded to the compoundrepresented by Formula (II) is bonded to the coordination site (forexample, an acid group ion site derived from an acid group) of thelow-molecular-weight compound used in the near-infrared-absorbingcompound (A1). When a plurality of the above-described bonds aregenerated, a structure in which the low-molecular-weight compound usedin the near-infrared-absorbing compound (A1) crosslinks side chains ofthe compound represented by Formula (II) through the metal ion isformed. Consequently, it is possible to further increase the content ofthe metal ion in the composition and to achieve highnear-infrared-shielding properties. In addition, when thenear-infrared-absorbing compound (B) is formulated into thenear-infrared-absorbing composition of the present invention, it ispossible to form a cured film in which the cross-linking structure doesnot easily collapse even after being heated and, consequently, the heatresistance is excellent.

In addition, when the near-infrared-absorbing compound (A1) and thenear-infrared-absorbing compound (B) are formulated into thenear-infrared-absorbing composition of the present invention, it ispossible to more easily adjust film properties to be desired, and thus,for example, it becomes possible to suppress cracking during formationof a film.

FIGS. 8 and 9 are imaginary views illustrating examples of anear-infrared-absorbing composition 1A including thenear-infrared-absorbing compound (A1) and the near-infrared-absorbingcompound (B). Reference sign “2” represents a copper ion, Reference sign“3” represents a main chain in the compound represented by Formula (II),Reference sign “4” represents a side chain in the compound representedby Formula (II), Reference sign “5” represents a site coordinated tocopper, and Reference sign “8” represents a site at which thecross-linking groups in the low-molecular-weight compound arecrosslinked with each other.

FIG. 1 is an imaginary view illustrating an example of thenear-infrared-absorbing composition lA including thenear-infrared-absorbing compound (A1) and the near-infrared-absorbingcompound (B). Reference sign “2” represents a copper ion, Reference sign“3” represents a main chain in the compound represented by Formula (II),Reference sign “4” represents a side chain in the compound representedby Formula (II), Reference sign “5” represents a site coordinated tocopper (for example, an acid group ion site derived from an acid group),and Reference sign “6” represents an n1-valent group in a compoundrepresented by Formula (I) below. As described above, a structure inwhich the low-molecular-weight compound crosslinks the side chains ofthe compound represented by Formula (II) through the copper ion 2 isformed.

The ratio (mass ratio) between the near-infrared-absorbing compound (A1)and the near-infrared-absorbing compound (B) formulated into thecomposition of the present invention is preferably in a range of 3:97 to70:30 and more preferably in a range of 5:95 to 50:50.

In addition, in a case in which the near-infrared-absorbing compositionof the present invention includes at least the near-infrared-absorbingcompound (A2), in the composition, the coordination site (for example,an acid group ion site derived from an acid group) to the metalcomponent in the compound represented by Formula (III) is bonded to ametal ion in the metal component (preferably a copper ion) (for example,a coordinate bond). Furthermore, the metal ion bonded to the compoundrepresented by Formula (III) is further bonded to the coordination siteto a metal component in another compound represented by Formula (III)(for example, an acid group ion site derived from an acid group). When aplurality of the above-described bonds are generated, a structure inwhich the compounds represented by Formula (III) are crosslinked witheach other through the metal ion is formed. Consequently, it is possibleto further increase the content of the metal ion in the composition andto maintain high near-infrared-shielding properties. In addition, theformed cross-linking structure does not easily collapse even after beingheated and, consequently, it is possible to form a cured film havingexcellent heat resistance.

FIG. 2 is an imaginary view illustrating an example of anear-infrared-absorbing composition 1B including at least thenear-infrared-absorbing compound (A2). Reference sign “2” represents acopper ion, Reference sign “5” represents a site coordinated to copper(for example, an acid group ion site derived from an acid group), andReference sign “7” represents an n1-valent group in the compoundrepresented by Formula (III). As described above, a structure in whichthe compounds represented by Formula (III) are crosslinked with eachother through the copper ion 2 is formed.

The content of copper in the near-infrared-absorbing composition of thepresent invention is preferably 2% by mass or higher and more preferably5% by mass or higher of the total amount of solid contents in thecomposition. In addition, the content thereof is preferably 50% by massor lower and more preferably 45% by mass or lower. Particularly, thecontent thereof is preferably in a range of 2% by mass to 50% by massand more preferably in a range of 5% by mass to 45% by mass.

<<Near-Infrared-Absorbing Compound (A1: Low-Molecular-Weight Type)>>

The near-infrared-absorbing compound (A1: low-molecular-weight type) isobtained from a reaction between a metal component and alow-molecular-weight compound which has a coordination site to a metalcomponent and a cross-linking group and has a molecular weight of 1800or lower or a salt thereof or a low-molecular-weight compound which hastwo or more coordination sites to a metal component and has a molecularweight of 1800 or lower or a salt thereof.

<<<Metal Component>>>

The metal component is not particularly limited as long as the metalcomponent reacts with the low-molecular-weight compound so as to becapable of Ruining a compound exhibiting near-infrared-absorbingproperties, and a compound including a divalent metal is more preferred.

The metal component is preferably cobalt, iron, nickel, or a coppercomponent and more preferably a copper component. As the coppercomponent used in the present invention, copper or a compound includingcopper can be used. As the compound including copper, a copper oxide ora copper salt can be used. The copper salt is preferably monovalent ordivalent copper and more preferably divalent copper. Examples of thecopper salt include copper carboxylate (for example, copper acetate,copper ethylacetoacetate, copper formate, copper benzoate, copperstearate, copper naphthenate, copper citrate, copper 2-ethylhexanoate,and the like), copper sulfonate (for example, copper methanesulfonateand the like), copper phosphate, copper phosphoric acid ester, copperphosphonate, copper phosphonic acid ester, copper phosphinate, copperamide, copper sulfonamide, copper imide, copper acyl sulfonimide, copperbissulfonimide, copper methide, alkoxycopper, phenoxycopper, copperhydroxide, copper carbonate, copper sulfate, copper nitrate, copperperchlorate, copper chloride, copper bromide, copper (meth)acrylate,copper chlorate, copper pyrophosphate, and the like. Particularly,copper hydroxide, copper acetate, copper chloride, copper formate,copper stearate, copper benzoate, copper ethylacetoacetate, copperpyrophosphate, copper naphthenate, copper citrate, copper nitrate,copper sulfate, copper carbonate, copper chlorate, copper(meth)acrylate, and copper perchlorate are preferred, copper hydroxide,copper acetate, copper chloride, copper sulfate, copper benzoate, andcopper (meth)acrylate are more preferred, and copper hydroxide, copperacetate, and copper sulfate are particularly preferred.

The content of metal in the metal component is preferably in a range of2% by mass to 90% by mass and more preferably in a range of 10% by massto 70% by mass. Only one metal component may be used or two or moremetal components may be used. Particularly, since an increase in thecontent of copper as the metal component improvesnear-infrared-shielding properties, the content of copper in terms of anelement is preferably 10% by mass or higher, more preferably 20% by massor higher, and still more preferably 30% by mass or higher of all solidcontents in the near-infrared-absorbing composition. The upper limit ofthe content of copper is preferably 70% by mass or lower and morepreferably 60% by mass or lower.

The amount of the copper component that is reacted with thelow-molecular-weight compound is preferably in a range of 0.01equivalents to 1 equivalent, more preferably in a range of 0.1equivalents to 0.8 equivalents, and still more preferably in a range of0.2 equivalents to 0.6 equivalents with respect to 1 equivalent of thecoordination site (for example, an acid group) in the compound. When theamount of copper in the copper component is set in the above-describedrange, there is a tendency that a cured film having more favorablenear-infrared-shielding properties is obtained.

<<Low-Molecular-Weight Compound having Coordination Site to MetalComponent and Cross-Linking Group and having Molecular Weight of 1800 orLower (hereinafter, also Referred to as a Low-Molecular-Weight Compound(a1))>>

Examples of the coordination site to the metal component in thelow-molecular-weight compound (a1) include coordination sites (forexample, a coordination site to be coordinated with an anion(specifically an acid group or a salt thereof) and a coordination siteto be coordinated with an unshared electron pair). Thelow-molecular-weight compound (a1) may have one or more coordinationsites.

Any anion may be used as the anion as long as the anion includes ananion that can be coordinated to the metal component, and, for example,the anion preferably includes an oxygen anion, a nitrogen anion, or asulfur anion.

The coordination site to be coordinated with an anion is preferably, forexample, at least one site selected from Group (AN) below.

Group (AN)

In Group (AN), X represents N or CR, and each of R's independentlyrepresents a hydrogen atom, an alkyl group, an alkenyl group, an alkynylgroup, an aryl group, or a heteroaryl group.

The alkyl group represented by R may have a linear shape, a branchedshape, or a cyclic shape, and preferably has a linear shape. The numberof carbon atoms in the alkyl group is preferably in a range of 1 to 10,more preferably in a range of 1 to 6, and still more preferably in arange of 1 to 4. Examples of the alkyl group include a methyl group. Thealkyl group may have a substituent, and examples of the substituentinclude a halogen atom, a carboxylic acid group, and a heterocyclicgroup. The heterocyclic group as the substituent may be a monocyclicring or a polycyclic ring and may be an aromatic group or a non-aromaticgroup. The number of hetero atoms constituting a heterocycle ispreferably in a range of 1 to 3 and preferably 1 or 2. The hetero atomconstituting the heterocycle is preferably a nitrogen atom. In a case inwhich the alkyl group has a substituent, the alkyl group may includeanother substituent.

The number of carbon atoms in the alkynyl group represented by R ispreferably in a range of 1 to 10 and more preferably in a range of 1 to6.

The aryl group represented by R may be a monocyclic ring or a polycyclicring and is preferably a monocyclic ring. The number of carbon atoms inthe aryl group is preferably in a range of 6 to 18, more preferably in arange of 6 to 12, and still more preferably 6.

The heteroaryl group represented by R may be a monocyclic ring or apolycyclic ring. The number of hetero atoms constituting the heteroarylgroup is preferably in a range of 1 to 3. The hetero atom constitutingthe heteroaryl group is preferably a nitrogen atom, an oxygen atom, or asulfur atom. The number of carbon atoms in the heteroaryl group ispreferably in a range of 6 to 18 and more preferably in a range of 6 to12.

Examples of the coordination site to be coordinated with an anion alsoinclude a monoanionic coordination site. The monoanionic coordinationsite represents a site to be coordinated to a metal atom through afunctional group having one negative charge. Examples thereof include anacid group having an acid dissociation constant (pKa) of 12 or lower,and specific examples thereof include an acid group having a phosphorusatom (a phosphate diester group, a phosphonate monoester group, or aphosphinic acid group), a sulfonic acid group, a carboxylic acid group,an imidic acid group, and the like. The monoanionic coordination sitepreferably includes at least one of a sulfonic acid group, a carboxylicacid group, an acid group having a phosphorus atom, and an imidic acidgroup and more preferably includes at least one of a sulfonic acidgroup, a carboxylic acid group, and an imidic acid group.

The coordination site to be coordinated with an unshared electron pairpreferably includes, as a coordinating atom, an oxygen atom, a nitrogenatom, a sulfur atom, or a phosphorus atom, more preferably includes anoxygen atom, a nitrogen atom, or a sulfur atom, and still morepreferably includes a nitrogen atom. In addition, an aspect in which acoordinating atom to be coordinated with an unshared electron pair is anitrogen atom and an atom adjacent to the nitrogen atom is a carbon atomis preferred, and the carbon atom preferably has a substituent. When theabove-described constitution is provided, the structure of a coppercomplex becomes more easily distorted, and thus it is possible tofurther improve color valency. The substituent is preferably an alkylgroup having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbonatoms, a carboxylic acid group, an alkoxy group having 1 to 12 carbonatoms, an acyl group having 2 to 12 carbon atoms, an alkylthio grouphaving 1 to 12 carbon atoms, or a halogen atom.

The coordinating atom to be coordinated with an unshared electron pairmay be included in a ring or may be included in at least one partialstructure selected from Group (UE) below.

Group (UE)

In Group (UE), each of R^(h)s independently represents a hydrogen atom,an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or aheteroaryl group, and each of R²'s independently represents a hydrogenatom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group,a heteroaryl group, an alkoxy group, an aryloxy group, a heteroaryloxygroup, an alkylthio group, an arylthio group, a heteroarylthio group, anamino group, and an acyl group.

The alkyl group represented by R¹ is identical to the alkyl groupdescribed in the section of R in Group (AN), and the preferred rangethereof is also identical.

The number of carbon atoms in the alkenyl group represented by R¹ ispreferably in a range of 1 to 10 and more preferably in a range of 1 to6.

The number of carbon atoms in the alkynyl group represented by R¹ ispreferably in a range of 1 to 10 and more preferably in a range of 1 to6.

The heteroaryl group represented by R¹ is identical to the heteroarylgroup described in the section of R in Group (AN), and the preferredrange thereof is also identical.

The alkyl group represented by R² is identical to the alkyl groupdescribed in the section of R¹ in Group (UE), and the preferred rangethereof is also identical.

The number of carbon atoms in the alkenyl group represented by R² ispreferably in a range of 1 to 10 and more preferably in a range of 1 to6.

The number of carbon atoms in the alkynyl group represented by R² ispreferably in a range of 1 to 10 and more preferably in a range of 1 to6.

The aryl group represented by R² is identical to the aryl groupdescribed in the section of R¹ in Group (UE), and the preferred rangethereof is also identical.

The heteroaryl group represented by R² is identical to the heteroarylgroup described in the section of R¹ in Group (UE), and the preferredrange thereof is also identical.

The number of carbon atoms in the alkoxy group represented by R² ispreferably in a range of 1 to 12.

The number of carbon atoms in the aryloxy group represented by R² ispreferably in a range of 6 to 18.

The heteroaryloxy group represented by R² may be a monocyclic ring or apolycyclic ring. A heteroaryl group constituting the heteroaryloxy groupis identical to the heteroaryl group described in the section of R¹ inGroup (UE), and the preferred range thereof is also identical.

The number of carbon atoms in the alkylthio group represented by R² ispreferably in a range of 1 to 12.

The number of carbon atoms in the arylthio group represented by R² ispreferably in a range of 6 to 18.

The heteroarylthio group represented by R² may be a monocyclic ring or apolycyclic ring. A heteroaryl group constituting the heteroarylthiogroup is identical to the heteroaryl group described in the section ofand the preferred range thereof is also identical.

The number of carbon atoms in the acyl group represented by R² ispreferably in a range of 2 to 12.

In a case in which the coordinating atom to be coordinated with anunshared electron pair is included in a ring, the ring including thecoordinating atom may be a monocyclic ring or a polycyclic ring and maybe aromatic or non-aromatic. The ring including the coordinating atom ispreferably a 5- to 12-membered ring, more preferably a 5- to 7-memberedring, and still more preferably a 5- or 6-membered ring.

The ring including the coordinating atom to be coordinated with anunshared electron pair may have a substituent. Examples of thesubstituent include a linear, branched, or cyclic alkyl group having 1to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, a halogenatom, a silicon atom, an alkoxy group having 1 to 12 carbon atoms, anacyl group having 1 to 12 carbon atoms, an alkylthio group having 1 to12 carbon atoms, and a carboxylic acid group. The substituent may haveanother substituent. Examples of the substituent include a group formedof a ring including a coordinating atom to be coordinated with anunshared electron pair, a group having at least one partial structureselected from Group (UE) described above, an alkyl group having 1 to 12carbon atoms, an acyl group having 1 to 12 carbon atoms, a hydroxygroup, and the like.

The low-molecular-weight compound (a1) may include one or morecross-slinking groups. The cross-linking group is not particularlylimited, but is preferably one or more groups selected from a(meth)acryloyloxy group, an epoxy group, an oxetanyl group, anisocyanate group, a hydroxyl group, an amino group, a carboxyl group, athiol group, an alkoxysilyl group, a methylol group, a vinyl group, a(meth)acrylamide group, a sulfo group, a styryl group, and a maleimidegroup, and more preferably one or more groups selected from a(meth)acryloyloxy group and a vinyl group. The number of thecross-linking groups may be one or more.

The low-molecular-weight compound (a1) is preferably a compoundrepresented by General Formula (a1-i) below.

R¹⁰⁰-L¹⁰⁰-(X¹⁰⁰)_(n)   (a1-i)

In Formula (a1-i), X¹⁰⁰ represents a coordination site to the metalcomponent, n represents an integer from 1 to 6, Coo represents a singlebond or a linking group, and R¹⁰⁰ represents a cross-linking group.

In Formula (a1-i), X¹⁰⁰ is preferably one or more sites selected from acoordination site to be coordinated with an anion (for example, an acidgroup or a salt thereof) and a coordination site to be coordinated withan unshared electron pair.

In General Formula (a1-i), n represents an integer from 1 to 6, and ispreferably an integer from 1 to 3 and more preferably an integer of 1 or2.

In General Formula (a1-i), L¹⁰⁰ represents a single bond or a linkinggroup. The linking group is preferably an organic group or a groupformed of a combination of an organic group and —O—, —SO—, —SO₂—,—NR^(N1)—, —CO—, or —CS—. Examples of the organic group include ahydrocarbon group, an oxyalkylene group, and a heterocyclic group. Inaddition, the linking group may be a group having at least onecoordination site selected from Group (AN-1) below, a ring having acoordinating atom coordinated with an unshared electron pair, or a grouphaving at least one partial structure selected from Group (UE-1) below.

The hydrocarbon group is preferably an aliphatic hydrocarbon group or anaromatic hydrocarbon group. The hydrocarbon group may have asubstituent, and examples of the substituent include an alkyl group, ahalogen atom (preferably a fluorine atom), a polymerizable group (forexample, a vinyl group, a (meth)acryloyl group, an epoxy group, anoxetane group, or the like), a sulfonic acid group, a carboxylic acidgroup, an acid group having a phosphorus atom, a carboxylic acid estergroup (for example, —CO₂CH₃), a hydroxyl group, an alkoxy group (forexample, a methoxy group), an amino group, a carbamoyl group, acarbamoyloxy group, a halogenated alkyl group (for example, afluoroalkyl group or a chloroalkyl group), and a (meth)acryloyloxygroup. In a case in which the hydrocarbon group has a substituent, thehydrocarbon group may have another substituent, and examples thereofinclude an alkyl group, the above-described polymerizable group, and ahalogen atom.

In a case in which the hydrocarbon group is monovalent, an alkyl group,an alkenyl group, or an aryl group is preferred, and an aryl group ismore preferred. In a case in which the hydrocarbon group is divalent, analkylene group, an arylene group, or an oxyalkylene group is preferred,and an arylene group is more preferred. In a case in which thehydrocarbon group is trivalent, groups corresponding to the monovalenthydrocarbon group or the divalent hydrocarbon group are preferred.

The alkyl group and the alkylene group may have any of a linear shape, abranched shape, and a ring shape. The number of carbon atoms in thelinear alkyl or alkylene group is preferably in a range of 1 to 20, morepreferably in a range of 1 to 12, and still more preferably in a rangeof 1 to 8. The number of carbon atoms in the branched alkyl or alkylenegroup is preferably in a range of 3 to 20, more preferably in a range of3 to 12, and still more preferably in a range of 3 to 8. The cyclicalkyl or alkylene group may be either a monocyclic ring or a polycyclicring. The number of carbon atoms in the cyclic alkyl or alkylene groupis preferably in a range of 3 to 20, more preferably in a range of 4 to10, and still more preferably in a range of 6 to 10.

The number of carbon atoms in the alkenyl group and the alkenylene groupis preferably in a range of 2 to 10, more preferably in a range of 2 to8, and still more preferably in a range of 2 to 4.

The number of carbon atoms in the aryl group or the arylene group ispreferably in a range of 6 to 18, more preferably in a range of 6 to 14,and still more preferably in a range of 6 to 10.

Examples of the heterocyclic group include a group having a hetero atomin an alicyclic group and an aromatic heterocyclic group. Theheterocyclic group is preferably a 5-membered ring or a 6-membered ring.In addition, the heterocyclic group is a monocyclic ring or a fusedring, is preferably a monocyclic ring or a fused ring having 2 to 8fused portions, and more preferably a monocyclic ring or a fused ringhaving 2 to 4 fused portions. The heterocyclic group may have asubstituent, and the substituent is identical to the substituent thatthe above-described hydrocarbon group may have.

In —NR^(N1)—, R^(N1) represents a hydrogen atom, an alkyl group, an arylgroup, or an aralkyl group. The alkyl group as R^(N1) may have any of alinear shape, a branched shape, and a ring shape. The number of carbonatoms in a linear or branched alkyl group is preferably in a range of 1to 20 and more preferably in a range of 1 to 12. The cyclic alkyl groupmay be either a monocyclic ring or a polycyclic ring. The number ofcarbon atoms in the cyclic alkyl group is preferably in a range of 3 to20 and more preferably in a range of 4 to 14.

The number of carbon atoms in the aryl group as R^(N1) is preferably ina range of 6 to 18 and more preferably in a range of 6 to 14. Specificexamples thereof include a phenyl group and a naphthyl group. Thearalkyl group as R^(N1) is preferably an aralkyl group having 7 to 20carbon atoms and more preferably an unsubstituted aralkyl group having 7to 15 carbon atoms.

Group (UE-1)

In Group (UE-1), R¹ is identical to R¹ in Group (UE).

Group (AN-1)

In Group (AN-1), X represents N or CR, and R is identical to R describedin the section of CR in Group (AN) described above.

In General Formula (a1-i), R¹⁰⁰ represents a cross-linking group and isidentical to the above-described cross-linking group, and the preferredrange thereof is also identical.

Examples of the low-molecular-weight compound (a1) include the followingcompounds. In specific examples below, n represents an integer from 1 to90.

In the following Table, for example, a compound L-1 represents acompound represented by the following general formula, R represents agroup including a cross-linking group shown in the vertical column, andY represents a coordination site to be coordinated to a metal componentshown in the horizontal row. In addition, * represents a bonding site.

TABLE 1

Y

R

L-1 L-8 L-15 L-22

L-2 L-9 L-16 L-23

L-3 L-10 L-17 L-24

L-4 L-11 L-18 L-25

L-5 L-12 L-19 L-26

L-6 L-13 L-20 L-27

L-7 L-14 L-21 L-28

TABLE 2

Y

R

L-29 L-36 L-43

L-30 L-37 L-44

L-31 L-38 L-45

L-32 L-39 L-46

L-33 L-40 L-47

L-34 L-41 L-48

L-35 L-42 L-49

TABLE 3

Y

R

L-50 L-57 L-64 L-71

L-51 L-58 L-65 L-72

L-52 L-59 L-66 L-73

L-53 L-60 L-67 L-74

L-54 L-61 L-68 L-75

L-55 L-62 L-69 L-76

L-56 L-63 L-70 L-77

TABLE 4

Y

R

L-78 L-85 L-92

L-79 L-86 L-93

L-80 L-87 L-94

L-81 L-88 L-95

L-82 L-89 L-96

L-83 L-90 L-97

L-84 L-91 L-98

TABLE 5

Y

R

L-99  L-106 L-113 L-120 L-127

L-100 L-107 L-114 L-121 L-128

L-101 L-108 L-115 L-122 L-129

L-102 L-109 L-116 L-123 L-130

L-103 L-110 L-117 L-124 L-131

L-104 L-111 L-118 L-125 L-132

L-105 L-112 L-119 L-126 L-133

TABLE 6

Y

R

L-134 L-141 L-148 L-155 L-162

L-135 L-142 L-149 L-156 L-163

L-136 L-143 L-150 L-157 L-164

L-137 L-144 L-151 L-158 L-165

L-138 L-145 L-152 L-159 L-166

L-139 L-146 L-153 L-160 L-167

L-140 L-147 L-154 L-161 L-168

TABLE 7

Y

R

L-169 L-176 L-183

L-170 L-177 L-184

L-171 L-178 L-185

L-172 L-179 L-186

L-173 L-180 L-187

L-174 L-181 L-188

L-175 L-182 L-189

TABLE 8

Y           R    

   

L-190 L-194 L-198

L-191 L-195 L-199

L-192 L-196 L-200

L-193 L-197 L-201 Y         R  

L-202 L-206

L-203 L-207

L-204 L-208

L-205 L-209

TABLE 9

Y               R  

L-210 L-214

L-211 L-215

L-212 L-216

L-213 L-217                           R        

     

L-218 L-222 L-226

L-219 L-223 L-227

L-220 L-224 L-228

L-221 L-225 L-229

TABLE 10

Y R

L-230 L-234 L-238

L-231 L-235 L-239

L-232 L-236 L-240

L-233 L-237 L-241

TABLE 11

Y R

L-242 L-249 L-256 L-263

L-243 L-250 L-257 L-264

L-244 L-251 L-258 L-265

L-245 L-252 L-259 L-266

L-246 L-253 L-260 L-267

L-247 L-254 L-261 L-268

L-248 L-255 L-262 L-269

TABLE 12

Y R

L-270 L-277 L-284

L-271 L-278 L-285

L-272 L-279 L-286

L-273 L-280 L-287

L-274 L-281 L-288

L-275 L-282 L-289

L-276 L-283 L-290

TABLE 13

Y         R  

L-291 L-298 L-305

L-292 L-299 L-306

L-293 L-300 L-307

L-294 L-301 L-308

L-295 L-302 L-309

L-296 L-303 L-310

L-297 L-304 L-311 Y         R

L-312 L-319

L-313 L-320

L-314 L-321

L-315 L-322

L-316 L-323

L-317 L-324

L-318 L-325

TABLE 14

Y R

L-326 L-333

L-327 L-334

L-328 L-335

L-329 L-336

L-330 L-337

L-331 L-338

L-332 L-339

TABLE 15

Y R

L-340 L-348 L-356

L-341 L-349 L-357

L-342 L-350 L-358

L-343 L-351 L-359

L-344 L-352 L-360

L-345 L-353 L-361

L-346 L-354 L-362

L-347 L-355 L-363

TABLE 16

Y R

L-364 L-372 L-380

L-365 L-373 L-381

L-366 L-374 L-382

L-367 L-375 L-383

L-368 L-376 L-384

L-369 L-377 L-385

L-370 L-378 L-386

L-371 L-379 L-387

<<Low-Molecular-Weight Compound having Two or more Coordination Sites toMetal Component and having Molecular Weight of 1800 or Lower(hereinafter, also Referred to as “Low-Molecular-Weight Compound(a2)”)>>

The coordination site to the metal component in the low-molecular-weightcompound (a2) is identical to the coordination site described in thesection of the low-molecular-weight compound (a1), and the preferredrange thereof is also identical.

The number of the coordination sites to the metal component in thelow-molecular-weight compound (a2) may be two or more, and is preferablyin a range of 2 to 6, more preferably in a range of 2 to 5, and stillmore preferably in a range of 2 to 4. In addition, thelow-molecular-weight compound (a2) may include the cross-linking groupdescribed in the section of the low-molecular-weight compound (a1).

The low-molecular-weight compound (a2) is preferably a compoundrepresented by Formula (I) below.

R¹(—X¹)_(n1)   (I)

In Formula (I), X¹ represents a coordination site, n1 represents aninteger from 2 to 6, and R¹ represents an n1-valent group.

In Formula (I), X¹ is identical to X¹⁰⁰ in Formula (a1-i) describedbelow and is preferably a coordination site to be coordinated with ananion and more preferably an acid group. The acid group is preferablythe above-described acid group having an acid dissociation constant(pKa) of 12 or lower and more preferably includes at least one of asulfonic acid group, a carboxylic acid group, and an imidic acid group.The number of kinds of X¹ may be one or more and is preferably two ormore.

In Formula (I), n1 is preferably an integer from 2 to 5 and morepreferably an integer from 2 to 4.

In Formula (I), R¹ is preferably an n1 -valent organic group or a groupfoimed of a combination of the nl-valent organic group and at least onegroup selected from —O—, —S—, —CO—, —SO—, —SO₂—, —CO—, and —CS— and ispreferably a hydrocarbon group or a group formed of a combination of thehydrocarbon group and at least one group selected from —O—, —S—, —CO—,—SO₂—, and —NR^(N1)—.

In a case in which n1 is 2, R¹ more preferably includes at least one ofan alkylene group, an alkenylene group, and an arylene group and isstill more preferably a group formed of a combination of theabove-described group and one group selected from —O—, —S—, —CO—, and—SO₂—. —NR^(N1)— is identical to —NR^(N1)— in General Formula (a1-i)described above.

In addition, the nl-valent group may be a group having at least onecoordination site selected from Group (AN-1) described above, a ringhaving a coordinating atom to be coordinated with an unshared electronpair, or a group having at least one partial structure selected fromGroup (UE-1) described above.

In a case in which n1 is 2, the alkylene group as R¹ may be a linear,branched, or cyclic alkylene group, but is preferably a linear orbranched alkylene group and more preferably a linear alkylene group. Thenumber of carbon atoms in the linear or branched alkylene group ispreferably in a range of 1 to 18, more preferably in a range of 1 to 12,and still more preferably in a range of 1 to 8.

In a case in which n1 is 2, the number of carbon atoms in the alkenylenegroup as R¹ is preferably in a range of 2 to 10, more preferably in arange of 2 to 8, and still more preferably in a range of 2 to 6.

In a case in which n1 is 2, the arylene group as R¹ is preferably anarylene group having 6 to 20 carbon atoms. The arylene group ispreferably a phenylene group or a naphthylene group and more preferablya 1,4-phenylene group or a 1,5-naphthylene group.

In a case in which n1 is 3 or greater, n1 is preferably represented byFormula (III) below.

Examples of a substituent that R¹ in Formula (I) may have include analkyl group, a polymerizable group (for example, a group having anunsaturated double bond (a vinyl group, a (meth)acryloyl group, an epoxygroup, an oxetane group, or the like)), a halogen atom, a carboxylicacid group, a carboxylic acid ester group (—CO₂CH₃ or the like), ahydroxyl group, an alkoxy group (for example, a methoxy group), an aminogroup, a carbamoyl group, a carbamoyloxy group, an amide group, ahalogenated alkyl group (a fluoroalkyl group, a chloroalkyl group, orthe like), a (meth)acryloyloxy group, and the like, and the substituentis preferably a halogen atom (particularly, a fluorine atom). In a casein which R¹ has a substituent, R¹ may have another substituent, andexamples of the substituent include an alkyl group, the above-describedpolymerizable group, a halogen atom, and the like.

The molecular weight of the compound represented by Formula (I) and asalt thereof is preferably in a range of 80 to 1800, more preferably ina range of 100 to 1500, and still more preferably in a range of 150 to1000.

Specific aspects of the low-molecular-weight compound (a2) include acompound including one or more coordination sites to be coordinated withan anion and one or more coordinating atoms to be coordinated with anunshared electron pair (hereinafter, also referred to as compound(a2-1)), a compound including two or more coordinating atoms to becoordinated with an unshared electron pair (hereinafter, also referredto as compound (a2-2)), a compound including two or more coordinationsites to be coordinated with an anion (hereinafter, also referred to ascompound (a2-3)), and the like. Each of these compounds can beindependently used or a combination of two or more compounds can beused.

<<<<Compound (a2-1)>>>>

In the compound (a2-1), the total number of coordination sites to becoordinated with an anion and coordinating atoms to be coordinated withan unshared electron pair in one molecule may be 2 or more and may be 3or 4.

The compound (a2-1) is preferably, for example, a compound representedby Formula (i-1) below.

X¹¹-L¹¹-Y¹¹

X¹¹ represents the coordination site represented by Group (AN) describedabove.

Y¹¹ represents the above-described ring including the coordinating atomto be coordinated with an unshared electron pair or the partialstructure represented by Group (UE).

L¹¹ represents a single bond or a divalent linking group. The divalentlinking group is preferably an alkylene group having 1 to 12 carbonatoms, an arylene group having 6 to 12 carbon atoms, —SO—, —SO₂—, —O—,or a group formed of a combination thereof.

More detailed examples of the compound (a2-1) also include compoundsrepresented by General Formulae (i-2) to (i-9) below.)

X¹²-L¹²-Y¹²-L¹³-X¹³   (i-₂)

Y¹³-L¹⁴-Y¹⁴-L¹⁵-X¹⁴   (i-3)

Y¹⁵-L¹⁶-X¹⁵-L¹⁷-X¹⁶   (i-4)

Y¹⁶-L¹⁸-X¹⁷-L¹⁹-Y¹⁷   (i-5)

X¹⁸-L²⁰-Y¹⁸-L²¹-Y¹⁹-L²²-X¹⁹   (i-6)

X²⁰-L²³-Y²⁰-L²⁴-Y²¹-L²⁵-Y²²   (i-7)

Y²³-L²⁶-X²¹-L²⁷-X²²-L²⁸-Y²⁴   (i-8)

Y²⁵-L²⁹-X²³-L³⁰-Y²⁶-L³¹-Y²⁷   (i-9)

In General Formulae (i-2) to (i-9), each of X¹² to X¹⁴, X¹⁶, and X¹⁸ toX²⁰ independently represents the coordination site represented by Group(AN) described above. In addition, each of X¹⁵, X¹⁷, and X²¹ to X²³independently represents the coordination site represented by Group(AN-1) described above.

In General Formulae (i-2) to (i-9), each of L¹² to L³¹ independentlyrepresents a single bond or a divalent linking group. The divalentlinking group is identical to that of a case in which L¹ in GeneralFormula (i-1) represents a divalent linking group.

The compound (a2-1) is also preferably a compound represented by Formula(i-10) or (i-11).

In Formula (i-10), X² represents a group including the coordination siteto be coordinated with an anion. Y² represents an oxygen atom, anitrogen atom, a sulfur atom, or a phosphorus atom. Each of A¹ and A⁵independently represents a carbon atom, a nitrogen atom, or a phosphorusatom. Each of A² to A⁴ independently represents a carbon atom, an oxygenatom, a nitrogen atom, a sulfur atom, or a phosphorus atom. R¹represents a substituent. R^(X2) represents a substituent. n2 representsan integer from 0 to 3.

In Formula (i-10), X² may be formed of only a group including thecoordination site to be coordinated with an anion and the groupincluding the coordination site to be coordinated with an anion may havea substituent. Examples of the substituent that the group including thecoordination site to be coordinated with an anion may have include ahalogen atom, a carboxylic acid group, and a heterocyclic group. Theheterocyclic group as the substituent may be a monocyclic ring or apolycyclic ring and may be an aromatic group or an non-aromatic group.The number of hetero atoms constituting the heterocyclic ring ispreferably in a range of 1 to 3. The hetero atom constituting theheterocyclic ring is preferably a nitrogen atom.

In Formula (i-10), Y² is preferably an oxygen atom, a nitrogen atom, ora sulfur atom, more preferably an oxygen atom or a nitrogen atom, andstill more preferably a nitrogen atom.

In Formula (i-10), A¹ and A⁵ are preferably carbon atoms.

In Formula (i-10), A² to A³ preferably represent carbon atoms. A⁴preferably represents a carbon atom or a nitrogen atom.

In Formula (i-10), R¹ is identical to the substituent that the ringincluding the above-described coordinating atom to be coordinated withan unshared electron pair may have.

In Formula (i-10), R^(X2) is identical to the substituent that theabove-described ring including the coordinating atom to be coordinatedwith an unshared electron pair may have, and the preferred range thereofis also identical.

In Formula (i-10), n2 represents an integer from 0 to 3, and ispreferably 0 or 1 and more preferably 0.

In the compound represented by Formula (i-10), the hetero ring includingY² may be a monocyclic structure or a polycyclic structure. Specificexamples of a monocyclic structure as the hetero ring including Y²include a pyridine ring, a pyridazine ring, a pyrimidine ring, apyrazine ring, a triazine ring, a pyran ring, and the like. Specificexamples of a polycyclic structure as the hetero ring including Y²include a quinoline ring, an isoquinoline ring, a quinoxaline ring, anacridine ring, and the like.

In Formula (i-11), X³ represents the above-described group having thecoordination site to be coordinated with an anion. Y³ represents anoxygen atom, a nitrogen atom, a sulfur atom, or a phosphorus atom. Eachof A⁶ and A⁹ independently represents a carbon atom, a nitrogen atom, ora phosphorus atom. Each of A⁷ to A⁸ independently represents a carbonatom, an oxygen atom, a nitrogen atom, a sulfur atom, or a phosphorusatom. R² represents a substituent. R^(X3) represents a substituent. n3represents an integer from 0 to 2.

In Formula (i-11), X³ is identical to X² in Formula (i-10), and thepreferred range thereof is also identical.

In Formula (i-11), Y³ is preferably an oxygen atom, a nitrogen atom, ora sulfur atom, and more preferably an oxygen atom or a nitrogen atom.

In Formula (i-11), A⁶ is preferably a carbon atom or a nitrogen atom. A⁹is preferably a carbon atom.

In Formula (i-11), A⁷ is preferably a carbon atom. A⁸ is preferably acarbon atom, a nitrogen atom, or a sulfur atom.

In Formula (i-11), R² is preferably a hydrophobic substituent, morepreferably a hydrocarbon group having 1 to 30 carbon atoms, still morepreferably an alkyl group having 3 to 30 carbon atoms or an aryl grouphaving 6 to 30 carbon atoms, and particularly preferably an alkyl grouphaving 3 to 15 carbon atoms.

In Formula (i-11), R^(X3) is identical to R^(X2) in Formula (i-10), andthe preferred range thereof is also identical.

In Formula (i-11), n3 is preferably 0 or 1 and more preferably 0.

In the compound represented by Formula (i-11), the hetero ring includingY³ may be a monocyclic structure or a polycyclic structure. Specificexamples of a monocyclic structure as the hetero ring including Y³include a pyrazole ring, an imidazole ring, a triazole ring, an oxazolering, a thiazole ring, an isothiazole ring, and the like. Specificexamples of a polycyclic structure as the hetero ring including Y³include an indole ring, an isoindole ring, a benzofuran ring, anisobenzofuran ring, and the like.

Particularly, the compound represented by Formula (i-11) is preferably acompound having a pyrazole ring and preferably includes a secondary ortertiary alkyl group at the fifth site of the pyrazole ring. In thepresent specification, the fifth site of the pyrazole ring in a case inwhich the compound represented by Formula (i-11) is a compound having apyrazole ring refers to the substitution position of R² in a case inwhich Y³ and A⁶ in Formula (i-11) represent nitrogen atoms and A⁷ to A⁹represent carbon atoms. The number of carbon atoms in the secondary ortertiary alkyl group at the fifth site of the pyrazole ring ispreferably in a range of 3 to 15 and more preferably in a range of 3 to12.

The molecular weight of the compound (a2-1) is preferably 1000 or lower,more preferably 750 or lower, still more preferably 600 or lower, andparticularly preferably 500 or lower. In addition, the molecular weightof the compound (a2-1) is preferably 50 or higher, more preferably 70 orhigher, and still more preferably 80 or higher.

Specific examples of the compound (a2-1) include the followingcompounds.

<<<<Salt of Compound (a2-1)>>>>

The salt of the compound (a2-1), that is, the compound including a saltof the coordination site to be coordinated with an anion is preferably,for example, a metal salt. A metal atom constituting the metal salt ispreferably an alkali metal atom or an alkaline-earth metal atom.Examples of the alkali metal atom include sodium, potassium, and thelike. Examples of the alkaline-earth metal atom include potassium,magnesium, and the like.

<<<<Compound (a2-2)>>>>

In the compound (a2-2), the number of the coordinating atoms to becoordinated with an unshared electron pair may be 2 or more or 3 ormore, and is preferably in a range of 2 to 4 in a molecule.

The compound (a2-2) is preferably a compound represented by GeneralFormula (ii-1) below.

Y⁴⁰-L⁴⁰-Y⁴¹   (ii-1)

In General Formula (ii-1), each of Y⁴⁰ and Y⁴¹ independently representsa ring including the coordinating atom to be coordinated with anunshared electron pair or the partial structure represented by Group(UE).

In General Formula (ii-1), L⁴⁰ represents a single bond or a divalentlinking group. In a case in which L⁴⁰ represents a divalent linkinggroup, an alkylene group having 1 to 12 carbon atoms, an arylene grouphaving 6 to 12 carbon atoms, —SO—, —O—, —SO₂—, or a group formed of acombination thereof is preferred, and an alkylene group having 1 to 3carbon atoms, a phenylene group, or —SO₂— is preferred.

More detailed examples of the compound (a2-2) also include compoundsrepresented by General Formula (ii-2) or (ii-3) below.

Y⁴²-L⁴¹-Y⁴³-L⁴²-Y⁴⁴   (ii-2)

Y⁴⁵-L⁴³-Y⁴⁶-L⁴⁴-Y⁴⁷-L⁴⁵-Y⁴⁸   (ii-3)

In General Formulae (ii-2) and (ii-3), each of Y⁴², Y⁴⁴, Y⁴⁵, and Y⁴⁸independently represents a ring including the coordinating atom to becoordinated with an unshared electron pair or the partial structurerepresented by Group (UE).

In addition, each of Y⁴³, Y⁴⁶, and Y⁴⁷ is independently a ring includingthe coordinating atom to be coordinated with an unshared electron pairor a partial structure represented by Group (UE-1) described above.

In General Formulae (ii-2) and (ii-3), each of L⁴¹ to L⁴⁵ independentlyrepresents a single bond or a divalent linking group. The divalentlinking group is identical to that of a case in which L⁴⁰ in GeneralFormula (ii-1) represents a divalent linking group, and the preferredrange thereof is also identical.

The molecular weight of the compound (a2-2) is preferably 1000 or lower,more preferably 750 or lower, still more preferably 600 or lower, andparticularly preferably 500 or lower. In addition, the molecular weightof the compound (a2-2) is preferably 50 or higher, more preferably 70 orhigher, and still more preferably 80 or higher.

Specific examples of the compound (a2-2) include the followingcompounds.

<<<<Compound (a2-3)>>>>

The compound (a2-3) has two or more coordination sites to be coordinatedwith an anion. The coordination site to be coordinated with an anion isidentical to the above-described coordination site to be coordinatedwith an anion.

The compound (a2-3) is preferably a compound represented by GeneralFormula (iii-1) below.)

X⁵⁰-L⁵⁰-X⁵¹

In General Formula (iii-1), each of X⁵⁰ and X⁵¹ represents thecoordination site to be coordinated with an anion, is identical to theabove-described coordination site to be coordinated with an anion, andis preferably a monoanionic coordination site.

In General Formula (iii-1), L⁵⁰ represents a single bond or a divalentlinking group. The divalent linking group is preferably an alkylenegroup having 1 to 20 carbon atoms, an alkenylene group having 2 to 10carbon atoms, an arylene group having 6 to 18 carbon atoms, aheterocyclic group, —O—, —S—, —CO—, or —CS—, —SO₂—, or a group formed ofa combination thereof. R^(N1) is preferably a hydrogen atom, an alkylgroup having 1 to 12 carbon atoms, an aryl group having 6 to 18 carbonatoms, or an aralkyl group having 7 to 20 carbon atoms.

The compound (a2-3) preferably includes at least one group selected froma sulfonic acid group, a carboxylic acid group, and an imidic acidgroup. When a compound including at least one group selected from asulfonic acid group, a carboxylic acid group, and an imidic acid groupis used, it is possible to further improve valency.

The molecular weight of the compound (a2-3) is preferably 1000 or lower,more preferably 750 or lower, still more preferably 600 or lower, andparticularly preferably 500 or lower. In addition, the molecular weightof the compound (a2-3) is preferably 50 or higher, more preferably 70 orhigher, and still more preferably 80 or higher.

In addition, the compound (a2-3) is also preferably alow-molecular-weight compound having a molecular weight of 1800 or lowerwhich is represented by Formula (III) below. That is, thenear-infrared-absorbing composition of the present invention may includethe near-infrared-absorbing compound (A2) obtained from a reaction witha low-molecular-weight compound having a molecular weight of 1800 orlower which is represented by Formula (III) below or a salt thereof.

R³(—X¹)_(n2)   (III)

In Formula (III), R³ represents an n2-valent group, X¹ represents acoordination site to the metal component, and n2 represents an integerfrom 3 to 6.

When the near-infrared-absorbing composition of the present inventionincludes the near-infrared-absorbing compound (A2), it is possible toform a cured film having excellent heat resistance while maintaininghigh infrared-shielding properties.

In Formula (III), R³ is identical to R¹ in Formula (I), and thepreferred range thereof is also identical.

In Formula (III), X¹ is identical to X¹ in Formula (I), and thepreferred range thereof is also identical.

In Formula (III), n2 is preferably an integer from 3 to 5 and morepreferably 3 or 4.

Formula (III) is preferably represented by Formula (IV) below.

In Formula (IV), R¹¹ is an (n3+n11)-valent group, R¹² is a single bond,a divalent hydrocarbon group, or a group formed of a combination of adivalent hydrocarbon group and at least one element selected from —O—,—S—, —CO—, —SO₂—, —NR—(R represents a hydrogen atom or an alkyl group),R¹³ is a hydrocarbon group, —OH, or a group formed of a combination of ahydrocarbon group and at least one element selected from —O—, —S—, —CO—,—SO₂—, —NR—(R represents a hydrogen atom or an alkyl group), and thelike), and X¹ is a coordination site.

In Formula (IV), the total of n3 and n11 is preferably 4. n3 ispreferably 3 or 4.

is preferably an aliphatic hydrocarbon group having 1 or 2 carbon atomsor an aromatic hydrocarbon group having 6 carbon atoms.

R¹² is preferably a single bond, an alkylene group, or a group formed ofa combination of an alkylene group and at least one of —O—, —S—, —CO—,and —SO₂—. The number of carbon atoms in the alkylene group ispreferably in a range of 1 to 6.

R¹³ is preferably an ethylene group or —OH.

X¹ is identical to X¹ in Formula (I), and the preferred range thereof isalso identical.

Specific examples of the compound (a2-3) include the following compoundsand compounds of a salt of an acid group in the following compound (forexample, the above-described metal salt), but the compound (a2-3) is notlimited thereto. In addition, specific examples of the compoundrepresented by Formula (III) include compounds having three or morecoordination sites to be coordinated with an anion (specifically, anacid group) out of the following specific examples.

<<Near-Infrared-Absorbing Compound (B: High-Molecular-Weight Type)>>

The near-infrared-absorbing compound (B) is obtained from a reactionbetween a metal component and the compound represented by Formula (II).

<<<Metal Component>>>

The metal component is not particularly limited as long as the metalcomponent is capable of reacting with the compound represented byFormula (II) and thus forming a compound exhibitingnear-infrared-absorbing properties and is identical to the metalcomponent used to obtain the above-described near-infrared-absorbingcompound (A1: low-molecular-weight type), and the preferred rangethereof is also identical.

<<<High-Molecular-Weight Compound having Repeating Unit Represented byFormula (II) or Salt thereof>>>

A high-molecular-weight compound or a salt thereof which is reacted withthe metal component has a repeating unit represented by Formula (II).

(in Fonnula (II), R² represents an organic group, Y¹ represents a singlebond or a divalent linking group, and X² represents a coordination siteto the metal component.)

In Formula (II), R² is preferably an aliphatic hydrocarbon group or agroup having an aromatic hydrocarbon group and/or an aromaticheterocyclic group.

In Formula (II), in a case in which Y¹ represents a divalent linkinggroup, examples thereof include a divalent hydrocarbon group, aheteroarylene group, —O—, —S—, —CO—, —COO—, —OCO—, —SO₂—, —NX—(Xrepresents a hydrogen atom or an alkyl group and is preferably ahydrogen atom), or a group formed of a combination thereof.

Examples of the divalent hydrocarbon group include linear, branched, orcyclic alkylene groups and arylene groups. The hydrocarbon group mayhave a substituent, but is preferably not substituted.

The number of carbon atoms in the linear alkylene group is preferably ina range of 1 to 30, more preferably in a range of 1 to 15, and stillmore preferably in a range of 1 to 6. In addition, the number of carbonatoms in the branched alkylene group is preferably in a range of 3 to30, more preferably in a range of 3 to 15, and still more preferably ina range of 3 to 6. The cyclic alkylene group may be either a monocyclicring or a polycyclic ring. The number of carbon atoms in the cyclicalkylene group is preferably in a range of 3 to 20, more preferably in arange of 4 to 10, and still more preferably in a range of 6 to 10.

The number of carbon atoms in the arylene group is preferably in a rangeof 6 to 18, more preferably in a range of 6 to 14, and still morepreferably in a range of 6 to 10, and a phenylene group is particularlypreferred.

The heteroarylene group is preferably a 5-membered ring or a 6-memberedring. In addition, the heteroarylene group may be a monocyclic ring or afused ring and is preferably a monocyclic ring or a fused ring having 2to 8 fused portions, and more preferably a monocyclic ring or a fusedring having 2 to 4 fused portions.

In Formula (II), X² is identical to X¹ in Formula (I) and is preferablya group having one or more selected from a coordination site to becoordinated to the metal component with an anion and a coordinating atomto be coordinated to the metal component with an unshared electron pair.The coordination site to be coordinated with an anion preferablyincludes at least one of a carboxylic acid group, a sulfonic acid group,and an imidic acid group. A carboxylic acid group and a sulfonic acidgroup are preferred, and a sulfonic acid group is more preferred.

In Formula (II), in a case in which X² represents a group having acoordinating atom to be coordinated with an unshared electron pair,examples of X² include groups represented by Formula (1a1) or (1a2)below.

*-L¹¹-(X¹¹)_(p)   (1a1)

*-L¹¹-(X^(11a)-L¹²-X¹¹)_(p)   (1a2)

“*” represents a bonding site with Y¹ in Formula (II).

L¹¹ represents a single bond or a (p+1)-valent linking group. In a casein which L¹¹ represents a divalent linking group, L¹¹ is preferably analkylene group having 1 to 12 carbon atoms, an arylene group having 6 to12 carbon atoms, —CO—, —COO—, —OCO—, —SO₂—, —O—, —NR¹⁰—(R¹⁰ represents ahydrogen atom or an alkyl group and is preferably a hydrogen atom), or agroup formed of a combination thereof.

In a case in which L¹¹ represents a tri- or higher-valent linking group,examples thereof include groups obtained by removing one or morehydrogen atoms from the groups exemplified as the above-describeddivalent linking group.

L¹² represents a single bond or a divalent linking group. Preferredexamples of the divalent linking group include the divalent linkinggroups described in the section of L¹¹. L¹² is more preferably a singlebond, an alkylene group, or a group formed of a combination of —NH— and—CO—.

X¹¹ represents a ring having a coordinating atom to be coordinated withan unshared electron pair or the partial structure represented by Group(UE) described above. In a case in which p represents an integer of 2 orhigher, a plurality of X¹¹'s may be identical to or different from eachother.

X^(11a) represents a ring having a coordinating atom to be coordinatedwith an unshared electron pair or at least one partial structureselected from Group (UE-1) described above. In a case in which prepresents an integer of 2 or higher, a plurality of X^(11a)'s may beidentical to or different from each other.

In Formulae (1a1) and (1a2), p represents an integer of 1 or higher andis preferably 2 or higher. The upper limit is, for example, preferably 5or lower and more preferably 3 or lower.

<<<<Group having One or more Coordinating Atoms to be Coordinated withUnshared Electron Pair and One or more Coordination Sites to beCoordinated with Anion>>>>

In Formula (II), in a case in which X² represents a group having one ormore coordinating atoms to be coordinated with an unshared electron pairand one or more coordination sites to be coordinated with an anion,examples of X² include groups represented by Formulae below.

*-L²¹-(X^(21a)-L²³-X²²)_(q)   (1b1)

*-L²¹-(X^(22a)-L²-X²¹)_(q)   (1b2)

*-L²²-(X²¹)_(q)(X²²)_(r)   (1b3)

*-L²²-(X^(21a)-L²³-X²²)_(q)(X²¹)_(r)   (1b4)

*-L²²-(X^(22a)-L²³-X²¹)_(q)(X²¹)_(r)   (1b5)

*-L²²-(X^(21a)-L²³-X²²)_(q)(X²²)_(r)   (1b6)

*-L22-(X^(22a)-L²³-X²¹)_(q)(X²²)_(r)   (1b7)

“*” represents a bonding site with Y¹ in Formula (II).

L²¹ represents a single bond or a (q+1)-valent linking group. L²¹ isidentical to L¹¹ in Formula (lal), and the preferred range thereof isalso identical.

L²² represents a single bond or a (q+r+1)-valent linking group. L²² isidentical to L¹¹ in Formula (1 al), and the preferred range thereof isalso identical.

L²³ represents a single bond or a divalent linking group. Preferredexamples of the divalent linking group include the divalent linkinggroups described in the section of L¹¹ in Formula (1 a1). L²³ is morepreferably a single bond, an alkylene group, or a group formed of acombination of —NH— and —CO—.

X²¹ represents a ring having a coordinating atom to be coordinated withan unshared electron pair or the partial structure represented by Group(UE) described above. In a case in which q and r represent integers of 2or higher, a plurality of X²¹'s may be identical to or different fromeach other.

X^(21a) represents a ring having a coordinating atom to be coordinatedwith an unshared electron pair or at least one partial structureselected from Group (UE-1) described above. In a case in which q and rrepresent integers of 2 or higher, a plurality of X^(21a)'s may beidentical to or different from each other.

X²² represents the partial structure represented by Group (AN) describedabove. In a case in which q and r represent integers of 2 or higher, aplurality of X²²'s may be identical to or different from each other.

X^(22a) represents at least one coordination site selected from Group(AN-1) described above.

q represents an integer of 1 or higher and is preferably in a range of 1to 5 and particularly preferably in a range of 1 to 3.

r represents an integer of 1 or higher and is preferably in a range of 1to 5 and particularly preferably in a range of 1 to 3.

q+r represents 2 or higher and is preferably in a range of 2 to 5 andparticularly preferably 2 or 3.

<<<<Group having Coordination Site to be Coordinated with Anion>>>>

In Formula (II), in a case in which X² represents a group having acoordination site to be coordinated with an anion, examples of X²include groups represented by Formula (1c1) or (1c2) below.

*-L³¹-(X¹¹)_(p)   (1c1)

*-L³¹-(X^(31a)-L³²-X³¹)_(p)   (1c2)

“*” represents a bonding site with Y¹ in Formula (II).

L³¹ represents a single bond or a (p+1)-valent linking group. In a casein which L³¹ is identical to L″ in Formula (lal), the preferred rangethereof is also identical.

L³² represents a single bond or a divalent linking group. The divalentlinking group is identical to L¹² in Formula (1a2), and the preferredrange thereof is also identical.

X³¹ represents the coordination site to be coordinated with an anion. Ina case in which p represents an integer of 2 or higher, a plurality ofX³¹'s may be identical to or different from each other.

X^(31a) represents at least one coordination site selected from Group(AN-1) described above. In a case in which p represents an integer of 2or higher, a plurality of X^(31a)'s may be identical to or differentfrom each other.

In Formulae (1c1) and (1c2), p represents an integer of 1 or higher andis preferably 2 or higher. The upper limit is, for example, preferably 5or lower and more preferably 3 or lower.

A first embodiment of the compound represented by Formula (II) is apolymer having a carbon-carbon bond at the main chain, preferably has arepeating unit represented by Formula (II-1A) below, and more preferablyhas a repeating unit represented by Formula (II-1B) below.

(In Formula (II-1A), R′ represents a hydrogen atom or a methyl group, L¹represents a single bond or a divalent linking group, and X¹ representsa coordination site to the metal component. In Formula (II-1B), R²represents a hydrogen atom or a methyl group, L² represents a divalentlinking group, and M¹ represents a hydrogen atom or an atom or an atomicgroup constituting a salt with a sulfonic acid group.)

In Formulae (II-1 A) and (II-1 B), each of R¹ and R² is preferablyindependently a hydrogen atom.

In Formulae (II-1A) and (II-1B), in a case in which each of L¹ and L²represents a divalent linking group, each of L¹ and L² is identical tothat of a case in which Y¹ represents a divalent linking group, and thepreferred range is also identical.

In Formula (II-1A), X¹ is identical to X¹ in Formula (I), and thepreferred range is also identical.

In Formula (II-1B), M′ is preferably a hydrogen atom.

The compound represented by Formula (II) may have a repeating unit otherthan the repeating unit represented by Formula (II-1A) or (II-1B).Regarding the repeating unit, Paragraphs “0068” to “0075” (“0112” to“0118” in the specification of the corresponding US2011/0124824A) ofJP2010-106268A can be referred to, the content of which is incorporatedinto the specification of the present application.

Preferred examples of the repeating unit include repeating unitsrepresented by Formula (II-1C) below.

In Formula (II-1C), R³ represents a hydrogen atom or a methyl group andis preferably a hydrogen atom.

Y² represents a single bond or a divalent linking group, and thedivalent linking group is identical to the divalent linking group inFormula (II-1A) described above. Particularly, Y2 is preferably —COO—,—CO—, —NH—, a linear or branched alkylene group, or a group formed of acombination thereof or a single bond.

In Formula (II-1C), X² represents —PO₃H—, —PO₃H₂, —OH, or —COOH, and ispreferably —COOH.

In a case in which the compound represented by Formula (II) includesother repeating units (preferably a repeating unit represented byFormula (II-1A) or (II-1B)), the molar ratio between the repeating unitrepresented by Formula (II-1A) or (II-1B) and the repeating unitrepresented by Formula (II-1C) is preferably in a range of 95:5 to 20:80and more preferably in a range of 90:10 to 40:60.

Specific examples of the first embodiment of the compound represented byFormula (II) include the following compounds and salts of the followingcompounds, but the first embodiment is not limited thereto.

TABLE 17 B-1

B-2

B-3

B-4

B-5

B-6

B-7

B-8

B-9

 B-10

 B-11

 B-12

 B-13

 B-14

 B-15

TABLE 18 B-16

B-17

B-18

B-19

B-20

B-21

B-22

TABLE 19 B-23

B-24

B-25

B-26

B-27

B-28

B-29

B-30

B-31

B-32

B-33

B-34

B-35

B-36

The first embodiment of the compound represented by Formula (II) isobtained from a polymerization reaction of monomers constituting theabove-described constitutional unit. The polymerization reaction can beperformed using a well-known polymerization initiator. As thepolymerization initiator, an azo polymerization initiator can be used,and specific examples thereof include a water-soluble azo polymerizationinitiator, an oil-soluble azo polymerization initiator, and ahigh-molecular-weight polymerization initiator. Only one polymerizationinitiator may be used, or two or more polymerization initiators may bejointly used.

As the water-soluble azo polymerization initiator, it is possible touse, for example, commercially available products VA-044, VA-046B, V-50,VA-057, VA-061, VA-067, VA-086, and the like (trade names: allmanufactured by Wako Pure Chemical Industries, Ltd.). As the oil-solubleazo polymerization initiator, it is possible to use, for example,commercially available products V-60, V-70, V-65, V-601, V-59, V-40,VF-096, VAm-110, and the like (trade names: all manufactured by WakoPure Chemical Industries, Ltd.). As the high-molecular-weightpolymerization initiator, it is possible to use, for example,commercially available products VPS-1001, VPE-0201, and the like (tradenames: all manufactured by Wako Pure Chemical Industries, Ltd.).

A second embodiment of the compound represented by Formula (II) includesa repeating unit represented by at least any one of Formulae (II-2A),(II-2B), and (II-2C).

(In Formula (II-2A), R¹ represents an aliphatic hydrocarbon group, Y¹represents a single bond or a divalent linking group, X¹ represents acoordination site to the metal component, and at least one of R¹ and Y¹is substituted with a fluorine atom.

In Formula (II-2B), R² represents an aliphatic hydrocarbon group, R³represents a hydrocarbon group, Y² represents a single bond or adivalent linking group, and at least one of R², R³, and Y² issubstituted with a fluorine atom.

In Formula (II-2C), Ar^(l) represents an aromatic hydrocarbon groupand/or an aromatic heterocyclic group, R⁴ represents an organic group,Y³ represents a single bond or a divalent linking group, X² represents acoordination site to the metal component, and at least one of Ar¹, R⁴,and Y³ is substituted with a fluorine atom.)

In Formulae (II-2A) and (II-2B), each of R¹ and R² independentlyrepresents an aliphatic hydrocarbon group, and examples thereof includelinear, branched, or cyclic alkyl groups. The number of carbon atoms inthe linear alkyl group is preferably in a range of 1 to 20, morepreferably in a range of 1 to 10, and still more preferably in a rangeof 1 to 6. The number of carbon atoms in the branched alkyl group ispreferably in a range of 3 to 20, more preferably in a range of 3 to 10,and still more preferably in a range of 3 to 6. The cyclic alkyl groupmay be either a monocyclic ring or a polycyclic ring. The number ofcarbon atoms in the cyclic alkyl group is preferably in a range of 3 to20, more preferably in a range of 4 to 10, and still more preferably ina range of 6 to 10.

In a case in which R¹ and R² have a substituent, examples thereofinclude a polymerizable group (preferably a polymerizable group having acarbon-carbon double bond), a halogen atom (a fluorine atom, a chlorineatom, a bromine atom, or an iodine atom), an alkyl group, a carboxylicacid ester group, a halogenated alkyl group, an alkoxy group, amethacryloyloxy group, an acryloyloxy group, an ether group, a sulfonylgroup, a sulfide group, an amide group, an acyl group, a hydroxy group,a carboxylic acid group, an aralkyl group, -Si-(OR^(N22))₃, and thelike, and a fluorine atom is particularly preferred. (R^(N22) representsan alkyl group, and the number of carbon atoms is preferably in a rangeof 1 to 3.)

In Formulae (II-2A) to (II-2C), in a case in which each of Y¹ to Y³independently represents a divalent linking group, the divalent linkinggroup is identical to the divalent linking group in Formula (II-1A).

Examples of the hydrocarbon group include linear, branched, or cyclicalkylene groups or arylene groups. The number of carbon atoms in thelinear alkylene group is preferably in a range of 1 to 20, morepreferably in a range of 1 to 10, and still more preferably in a rangeof 1 to 6. The number of carbon atoms in the branched alkylene group ispreferably in a range of 3 to 20, more preferably in a range of 3 to 10,and still more preferably in a range of 3 to 6. The cyclic alkylenegroup may be either a monocyclic ring or a polycyclic ring. The numberof carbon atoms in the cyclic alkylene group is preferably in a range of3 to 20, more preferably in a range of 4 to 10, and still morepreferably in a range of 6 to 10.

The arylene group and the heteroarylene group are identical to those ina case in which the divalent linking group in Formula (II-1A) is anarylene group, and the preferred range thereof is also identical.

In the present invention, particularly, in a case in which Y¹ representsa divalent linking group, the divalent linking group is preferably—COO—, —CO—, —O—, —NX—(X represents a hydrogen atom or an alkyl groupand is preferably a hydrogen atom), a hydrocarbon group (preferably analkylene group or arylene group having 1 to 30 carbon atoms), or a groupformed of a combination thereof.

In Formulae (II-2A) to (II-2C), in a case in which each of X¹ and X²independently represents a coordination site to the metal component, thecoordination site to the metal component is identical to theabove-described coordination site to the metal component, and thepreferred range thereof is also identical.

In addition, in Formula (II-2A), at least one of R¹ and Y¹ issubstituted with a fluorine atom, and, out of R¹ and Y¹, at least Y¹ ispreferably substituted with a fluorine atom. Here, R¹ being substitutedwith a fluorine atom means that at least one of hydrogen atomsconstituting R¹ is substituted with a fluorine atom. At least one of R¹and Y¹ is preferably a perfluoro group.

In Formula (II-2B), R³ represents a hydrocarbon group, and examplesthereof include the alkyl group described in the section of R¹ inFormula (II-2A) and an aryl group. The alkyl group is identical to thealkyl group described in the section of R¹ in Formula (II-2A), and thepreferred range thereof is also identical. The number of carbon atoms inthe aryl group is preferably in a range of 6 to 18, more preferably in arange of 6 to 14, and more preferably in a range of 6 to 10. In a casein which R³ has a substituent, a fluorine atom is preferred.

In Formula (II-2B), it is preferable that at least one of R², R³, and Y²has a fluorine atom and at least one of R², R³, and Y² is a perfluorogroup.

In Formula (II-2C), Ar¹ preferably represents an aromatic hydrocarbongroup. The aromatic hydrocarbon group is preferably an aryl group having6 to 20 carbon atoms and more preferably a phenyl group or a biphenylgroup. The aromatic heterocyclic group is preferably an aromaticheterocyclic group having 2 to 30 carbon atoms.

In Formula (II-2C), R⁴ represents an organic group, and examples thereofinclude an alkylene group having 1 to 6 carbon atoms, a cycloalkylenegroup having 1 to 6 carbon atoms, —O—, —SO₂—, —CO—, —NR_(N)—(R_(N)represents a hydrogen atom or an alkyl group), and a combinationthereof. In a case in which R⁴ is an alkylene group, an alkyl grouphaving one carbon atom is preferred, and a group represented by—C(R^(4A))(R^(4B))— is more preferred. Each of R^(4A) and R^(4B)independently represents a fluorine atom or an alkyl group (preferablyan alkyl group having 1 to 3 carbon atoms), and the alkyl group may besubstituted with a fluorine atom. In a case in which R⁴ includes—C(R^(4A))(R^(4B))—, R^(4A) and R^(4B) may bond to each other and thusfaun a ring.

In a case in which R⁴ is a cycloalkylene group, cycloalkylene groupshaving 4 carbon atoms are preferred, and, among these, aperfluorocyclobutylene group is preferred.

Preferred examples of R⁴ include —C(R^(4A))(R^(4B))—, —O—, —CO—, and—SO₂—.

In Formula (II-2C), at least one of Ar¹, R⁴, and Y³ has a fluorine atom,and at least one of Ar', R⁴, and Y³ is preferably a perfluoro group.

In addition, the repeating unit represented by Formula (II-2C) may haveone or more of each of Ar¹ and R⁴ in the repeating unit and may have twoor more of each thereof.

The weight-average molecular weight of the polymer is preferably 2000 orhigher, more preferably in a range of 2000 to 2,000,000, and still morepreferably in a range of 5,000 to 400,000.

Specific examples of the second embodiment of the compound representedby Formula (II) include the following compounds and salts of thefollowing compounds, but the second embodiment is not limited thereto.In addition, additionally, a perfluorocarbonsulfonic acid polymerrepresented by NAFION (registered trade mark) can also be used.

A third embodiment of the compound represented by Formula (II) is anaromatic group-containing polymer.

A preferred example of the aromatic group-containing polymer preferablyincludes a repeating unit represented by Formula (II-3) below.

(In Formula (II-3), Ar¹ represents an aromatic hydrocarbon group and/oran aromatic heterocyclic group, Y¹ represents a single bond or adivalent linking group, and X¹ represents a coordination site to themetal component.)

In Formula (II-3), in a case in which Ar¹ represents an aromatichydrocarbon group, the aromatic hydrocarbon group is preferably an arylgroup. The number of carbon atoms in the aryl group is preferably in arange of 6 to 20, more preferably in a range of 6 to 15, and still morepreferably in a range of 6 to 12. The aromatic hydrocarbon group may bea monocyclic ring or a polycyclic ring, but is preferably a monocyclicring. Specifically, the aryl group is preferably a phenyl group, anaphthyl group, or a biphenyl group.

In Formula (II-3), in a case in which Ar¹ represents an aromaticheterocyclic group, the aromatic heterocyclic group is preferably anaromatic heterocyclic group having 2 to 30 carbon atoms. The aromaticheterocyclic group is preferably a monocyclic ring or a fused ring of a5-membered ring or a 6-membered ring and more preferably a monocyclicring or a fused ring having 2 to 8 fused portions. Examples of thehetero atom included in the heterocycle include nitrogen, oxygen, andsulfur atoms, and the hetero atom is more preferably nitrogen or oxygen.

Ar¹ may have a substituent T below other than —Y¹—X¹ in Formula (II-3).

Examples of the substituent T include an alkyl group, a polymerizablegroup (preferably a polymerizable group having a carbon-carbon doublebond), a halogen atom (a fluorine atom, a chlorine atom, a bromine atom,or an iodine atom), a carboxylic acid ester group, a halogenated alkylgroup, an alkoxy group, a methacryloyloxy group, an acryloyloxy group,an ether group, a sulfonyl group, a sulfide group, an amide group, anacyl group, a hydroxy group, a carboxylic acid group, and an aralkylgroup, and an alkyl group (particularly, an alkyl group having 1 to 3carbon atoms) is preferred.

Particularly, the aromatic group-containing polymer is preferably atleast one polymer selected from a polyether sulfone-based polymer, apolysulfone-based polymer, a polyether ketone-based polymer, apolyphenylene ether-based polymer, a polyimide-based polymer, apolybenzimidazole-based polymer, a polyphenylene-based polymer, a phenolresin-based polymer, a polycarbonate-based polymer, a polyamide-basedpolymer, and a polyester-based polymer. Hereinafter, examples of therespective polymers will be described.

Polyether sulfone-based polymer: a polymer having a main chain structure/represented by (—O-Ph-SO₂-Ph-) (Ph represents a phenylene group, whichshall apply below)

Polysulfone-based polymer: a polymer having a main chain structurerepresented by (—O-Ph-Ph-O-Ph-SO₂-Ph-)

Polyether ketone-based polymer: a polymer having a main chain structurerepresented by (—O-Ph-O-Ph-C(═O)-Ph-)

Polyphenylene ether-based polymer: a polymer having a main chainstructure represented by (-Ph-O—, -Ph-S—)

Polyphenylene-based polymer: a polymer having a main chain structurerepresented by (-Ph-)

Phenol resin-based polymer: a polymer having a main chain structurerepresented by (-Ph(OH)—CH₂—)

Polycarbonate-based polymer: a polymer having a main chain structurerepresented by (-Ph-O—C(═O)—O—)

as the polyamide-based polymer, for example, a polymer having a mainchain structure represented by (—Ph-C(═O)—NH—)

as the polyester-based polymer, for example, a polymer having a mainchain structure represented by (-Ph-C(═O)O—)

Regarding the polyether sulfone-based polymer, the polysulfone-basedpolymer, and the polyether ketone-based polymer, for example, the mainchain structures described in Paragraph “0022” of JP2006-310068A andParagraph “0028” of JP2008-27890A can be referred to, and the contentthereof is incorporated into the present specification.

Regarding the polyimide-based polymer, the main chain structuresdescribed in Paragraphs “0047” to “0058” of JP2002-367627A and “0018”and “0019” of JP2004-35891A can be referred to, and the content thereofis incorporated into the present specification.

In Formula (II-3), Y¹ is preferably a single bond. In a case in which Y¹represents a divalent linking group, the divalent linking group isidentical to Y¹ in Formula (II).

In a case in which Y¹ is a linear alkylene group, the number of carbonatoms in the linear alkylene group is preferably in a range of 1 to 20,more preferably in a range of 1 to 10, and still more preferably in arange of 1 to 6. In a case in which Y¹ is a branched alkylene group, thenumber of carbon atoms in the branched alkylene group is preferably in arange of 3 to 20, more preferably in a range of 3 to 10, and still morepreferably in a range of 3 to 6. In a case in which Y¹ is a cyclicalkylene group, the cyclic alkylene group may be either a monocyclicring or a polycyclic ring. The number of carbon atoms in the cyclicalkylene group is preferably in a range of 3 to 20, more preferably in arange of 4 to 10, and still more preferably in a range of 6 to 10.

The arylene group is identical to that of a case in which the divalentlinking group in Formulae (II-2A) to (II-2C) is an arylene group.

In Formula (II-3), the coordination site to the metal component which isrepresented by X¹ is identical to the above-described coordination siteto the metal component, and the preferred range thereof is alsoidentical.

Specific examples of the third embodiment of the compound represented byFormula (II) include the following compounds and compounds of a salt ofthe following acid groups, but the third embodiment is not limitedthereto.

The near-infrared-absorbing composition of the present inventionpreferably includes a near-infrared-absorbing compound (C) having apartial structure represented by Formula (IV) below.

(In Formula (IV), R⁴ represents an organic group, R⁵ represents adivalent group, Y² represents a single bond or a divalent linking group,each of X³ and X⁴ independently represents a site at which a coordinatebond is formed with copper, and Cu represents a copper ion.)

In Formula (IV), R⁴ is identical to R² in (II), and the preferred rangethereof is also identical.

In Formula (IV), R⁵ is identical to that of a case in which R¹ in (I)represents a divalent linking group, and the preferred range thereof isalso identical.

In Formula (IV), Y² is identical to Y² in (II), and the preferred rangethereof is also identical.

In Formula (IV), X³ is preferably an acid group ion site derived from anacid group and more preferably an acid group ion site derived from X¹ inFormula (I) (a group obtained by removing a hydrogen atom from X¹). InFormula (IV), X⁴ is preferably an acid group ion site derived from X² inFormula (II).

<Near-infrared-absorbing composition including near-infrared-absorbingcompound (A2: low-molecular-weight type)>

<<Near-Infrared-Absorbing Compound (A2)>>

The near-infrared-absorbing compound (A2) is obtained from a reactionbetween a metal component and a compound represented by Formula (III).

The metal component is not particularly limited as long as the metalcomponent is capable of reacting with the compound represented byFormula (III) and thus forming a compound exhibitingnear-infrared-absorbing properties and is identical to the metalcomponent used to obtain the above-described near-infrared-absorbingcompound (A1: low-molecular-weight type), and the preferred rangethereof is also identical.

The near-infrared-absorbing composition of the present invention mayinclude at least one of the near-infrared-absorbing compound (A1:low-molecular-weight type), the near-infrared-absorbing compound (B:high-molecular-weight type), and the near-infrared-absorbing compound(A2: low-molecular-weight type), and, if necessary, anothernear-infrared-absorbing compound, a solvent, a curable compound, abinder polymer, a surfactant, a polymerization initiator, and othercomponents may be formulated thereinto.

<<Another Near-Infrared-Absorbing Compound>>

In the composition of the present invention, for the purpose of furtherimproving a near-infrared-absorbing function, anothernear-infrared-absorbing compound other than the near-infrared-absorbingcompound (A1), the near-infrared-absorbing compound (B), and thenear-infrared-absorbing compound (A2) (hereinafter, also referred to asnear-infrared-absorbing compounds used in the present invention) may beformulated. The another near-infrared-absorbing compound is notparticularly limited as long as the another near-infrared-absorbingcompound has a maximum absorption wavelength in a range of generally 700nm to 2500 nm and preferably 700 nm to 1000 nm (near-infrared range).

The another near-infrared-absorbing compound is preferably a coppercompound and more preferably a copper complex. In addition, in a case inwhich the another near-infrared-absorbing compound is formulated intothe composition, the ratio (mass ratio) between thenear-infrared-absorbing compound and the another near-infrared-absorbingcompound which are used in the present invention is preferably in arange of 60:40 to 95:5 and more preferably in a range of 70:30 to 90:10.

In a case in which the another near-infrared-absorbing compound is acopper complex, a ligand L to be coordinated to copper is notparticularly limited as long as the ligand is capable of forming acoordinate bond with a copper ion, and examples thereof includecompounds having a sulfonic acid, a carboxylic acid, a phosphoric acid,a phosphoric acid ester, a phosphonic acid, a phosphonic acid ester, aphosphinic acid, a substituted phosphinic acid, a carbonyl (ester,ketone), an amine, an amide, a sulfone amide, urethane, urea, analcohol, or a thiol.

Specific examples of the copper complex include phosphorus-containingcopper compounds, sulfonic acid copper compounds, and copper compoundsrepresented by Formula (A). Regarding the phosphorus-containing coppercompound, specifically, for example, the compounds described in Row 27on Page 5 to Row 20 on Page 7 in W02005/030898A can be referred to, andthe content thereof is incorporated into the specification of thepresent application.

Examples of the copper complex include copper complexes represented byFormula (A) below.

Cu(X)_(n1)   Formula (A)

In Formula (A), X represents a ligand coordinated to copper, and each ofn1's independently represents an integer from 1 to 6.

The ligand X is a coordination site which is coordinated to copper andhas, for example, a substituent including C, N, O, and S as an atomcapable of being coordinated to copper and more preferably has a grouphaving a lone electron pair such as N, O, or S. The number of kinds ofthe coordination sites in the molecule is not limited to one and may betwo or more, and the coordination site may or may not be dissociated.

The copper complex is a copper compound in which a copper central metalis coordinated with a ligand, and copper is generally divalent copper.The copper complex can be obtained by, for example, mixing, andreacting, a compound or a salt thereof which serves as the ligand withthe copper component.

The compound or the salt thereof which serves as the ligand preferablyincludes a coordination site (for example, a coordination site to becoordinated with an anion or a coordination site to be coordinated witha lone electron pair), and preferred examples thereof include organicacid compounds (for example, a sulfonic acid compound and a carboxylicacid compound), salts thereof, and the like.

Particularly, a sulfonic acid compound represented by Formula (J) belowor a salt thereof is preferred.

In Formula (J), R⁷ represents a monovalent organic group.

A specific monovalent organic group is not particularly limited, andexamples thereof include linear, branched, or cyclic alkyl groups,alkenyl group, and aryl groups. Here, these groups may be groups througha divalent linking group (for example, an alkylene group, acycloalkylene group, an arylene group, —O—, —S—, —CO—, —C(═O)O—, —OCO—,—SO₂—, —NR—(R represents a hydrogen atom or an alkyl group), or thelike). In addition, the monovalent organic group may have a substituent.

The linear or branched alkyl group is preferably an alkyl group having 1to 20 carbon atoms, more preferably an alkyl group having 1 to 12 carbonatoms, and still more preferably an alkyl group having 1 to 8 carbonatoms.

The cyclic alkyl group may be either a monocyclic ring or a polycyclicring. The cyclic alkyl group is preferably a cycloalkyl group having 3to 20 carbon atoms, more preferably a cycloalkyl group having 4 to 10carbon atoms, and still more preferably a cycloalkyl group having 6 to10 carbon atoms. The alkenyl group is preferably an alkenyl group having2 to 10 carbon atoms, more preferably an alkenyl group having 2 to 8carbon atoms, and still more preferably an alkenyl group having 2 to 4carbon atoms.

The aryl group is preferably an aryl group having 6 to 18 carbon atoms,more preferably an aryl group having 6 to 14 carbon atoms, and stillmore preferably an aryl group having 6 to 10 carbon atoms.

Examples of the alkylene group, the cycloalkylene group, and the arylenegroup which are divalent linking groups include divalent linking groupsderived by removing one hydrogen atom from the alkyl group, thecycloalkyl group, and the aryl group.

Examples of the substituent that the monovalent organic group may haveinclude alkyl groups, polymerizable groups (for example, a vinyl group,a (meth)acryloyl group, an epoxy group, an oxetane group, and the like),halogen atoms, carboxylic acid groups, carboxylic acid ester groups (forexample, —CO₂CH₃ and the like), hydroxyl groups, amide groups,halogenated alkyl groups (for example, a fluoroalkyl group and achloroalkyl group), and the like.

The molecular weight of the sulfonic acid compound represented byFormula (J) below or a salt thereof is preferably in a range of 80 to750, more preferably in a range of 80 to 600, and still more preferablyin a range of 80 to 450.

Specific examples of the sulfonic acid compound represented by Formula(J) will be illustrated below, but the sulfonic acid compound is notlimited thereto.

As the sulfonic acid compound, a commercially available sulfonic acidcan also be used and can also be synthesized with reference to awell-known method. Examples of the salt of the sulfonic acid compoundinclude metal salts, and specific examples thereof include sodium salts,potassium salts, and the like.

As the copper compound, in addition to the above-described coppercompound, a copper compound for which a carboxylic acid is used as aligand may be used. For example, a compound represented by Formula (K)below can be used.

In Formula (K), R¹ represents a monovalent organic group. The monovalentorganic group is not particularly limited and is identical to, forexample, the monovalent organic group in Formula (J).

Specific examples of the compound represented by Formula (K) below willbe illustrated below, but the compound is not limited thereto.

The composition of the present invention may include inorganic fineparticles as another near-infrared-absorbing compound. Only one kind ofinorganic fine particles may be used or two or more kinds of inorganicfine particles may be used.

The inorganic fine particles refer to particles that play a role ofshielding (absorbing) infrared rays. The inorganic fine particles arepreferably at least one selected from the group consisting of metaloxide particles and metal particles in tetuis of more favorable infraredshielding properties.

Examples of the inorganic fine particles include metal oxide particlessuch as indium tin oxide (ITO) particles, antimony tin oxide (ATO)particles, particles of zinc oxide which may be doped with aluminum (ZnOwhich may be doped with aluminum), fluorine-doped tin dioxide (F-dopedSnO₂) particles, and niobium-doped titanium dioxide (Nb-doped TiO₂) andmetal particles such as silver (Ag) particles, gold (Au) particles,copper (Cu) particles, and nickel (Ni) particles. Meanwhile, in order tosatisfy both infrared shielding properties and photolithographicproperties, inorganic fine particles having a high transmittance at anexposure wavelength (365 nm to 405 nm) are desired and indium tin oxide(ITO) particles or antimony tin oxide (ATO) particles are preferred.

The shapes of the inorganic fine particles are not particularly limited,may be any of non-spherical and spherical, and may be sheet shapes, wireshapes, or tube shapes.

In addition, as the inorganic fine particles, a tungsten oxide-basedcompound can be used and, specifically, the inorganic fine particles aremore preferably a tungsten oxide-based compound represented by GeneralFormula (Composition Formula) below.

M_(x)W_(y)O_(z)

M represents a metal, W represents tungsten, and O represents oxygen.

0.001≦x/y≦1.1

2.2≦z/y≦3.0

Examples of the metal M include alkali metals, alkaline earth metals,Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al,Ga, In, Tl, Sn, Pb, Ti, Nb, V, Mo, Ta, Re, Be, Hf, Os, and Bi. The metalM is preferably an alkali metal, preferably Rb or Cs, and morepreferably Cs. The number of the metals M may be one or more.

When x/y is 0.001 or more, it is possible to sufficiently shieldinfrared rays and, when x/y is 1.1 or less, it is possible to morereliably avoid the generation of impurity phases in the tungstenoxide-based compound.

When z/y is 2.2 or more, it is possible to further improve chemicalstability as a material and, when z/y is 3.0 or less, it is possible tosufficiently shield infrared rays.

The metal oxide is preferably cesium tungsten oxide.

Specific examples of the tungsten oxide-based compound includeCs_(0.33)WO₃, Rb_(0.33)WO₃, K_(0.33)WO₃, Ba_(0.33)WO₃, and the like,Cs_(0.33)WO₃ or Rb_(0.33)WO₃ is preferred, and Cs_(0.33)WO₃ is morepreferred.

The metal oxide preferably has a fine particle form. The averageparticle diameter of the metal oxide is preferably 800 nm or less, morepreferably 400 nm or less, and still more preferably 200 nm or less.When the average particle diameter is in the above-described range, themetal oxide is not capable of easily shielding visible light throughlight scattering and thus it is possible to more reliably transmit lightin the visible light range. From the viewpoint of avoiding lightscattering, the average particle diameter is preferably small; however,in consideration of ease of handling during the production of the metaloxide, the average particle diameter of the metal oxide is generally 1nm or more.

The tungsten oxide-based compound can be produced in a form of, forexample, a dispersion of tungsten fine particles such as YMF-02,YMF-02A, YMS-01A-2, or YMF-10A-1 manufactured by Sumitomo Metal MiningCo., Ltd.

The content of the metal oxide is preferably in a range of 0.01% by massto 30% by mass, more preferably in a range of 0.1% by mass to 20% bymass, and still more preferably in a range of 1% by mass to 10% by massin relation to the total solid content mass of the composition includingthe metal oxide.

<Solvent>

Regarding a solvent used in the present invention, there is noparticular limitation, any solvent can be appropriately selecteddepending on the purpose as long as the solvent is capable of uniformlydissolving or dispersing the respective components of the composition ofthe present invention, and preferred examples thereof include aqueoussolvents such as water and alcohols (for example, ethanol). In addition,additional preferred examples of the solvent used in the presentinvention include organic solvents, alcohols, ketones, ethers, esters,aromatic hydrocarbons, halogenated hydrocarbons, dimethylformamide,dimethylacetamide, dimethylsulfoxide, sulfolane, and the like. Only onesolvent may be used, or two or more solvents may be jointly used.

Specific examples of the alcohols, the aromatic hydrocarbons, and thehalogenated hydrocarbons include those described in Paragraph “0136” andthe like in JP2012-194534A and the content thereof is incorporated intothe specification of the present application. In addition, specificexamples of the esters, the ketones, and the ethers include thosedescribed in Paragraph “0497” in JP2012-208494A (Paragraph “0609” in thecorresponding US2012/0235099A) and further include n-amyl acetate, ethylacetate, ethyl propionate, dimethyl phthalate, ethyl benzoate, methylsulfate, acetone, methyl isobutyl ketone, diethyl ether, ethylene glycolmonobutyl ether acetate, cyclopentanone, propylene glycol monomethylether, propylene glycol methyl ether acetate, and the like.

The content of the solvent is preferably in a range of 5% by mass to 60%by mass and more preferably in a range of 10% by mass to 40% by mass ofthe total solid contents of the composition of the present invention.

The composition of the present invention particularly preferablyincludes water. The content of water is preferably 10% by mass orhigher, more preferably 20% by mass or higher, still more preferably 30%by mass or higher, and far still more preferably 40% by mass or higherof the composition of the present invention. Particularly, the contentof water is preferably in a range of 40% by mass to 95% by mass and morepreferably in a range of 50% by mass to 90% by mass of the compositionof the present invention.

In a case in which the composition of the present invention includes asolvent other than water, the content of the solvent is preferably 5% bymass or higher of the composition of the present invention.Particularly, the content thereof is preferably in a range of 5% by massto 50% by mass and more preferably in a range of 5% by mass to 30% bymass of the composition of the present invention. Only one solvent otherthan water may be used, or two or more solvents may be used.

In a case in which water and an organic solvent are jointly used as thesolvents, the mass ratio between water and the organic solvent ispreferably in a range of 0.1:99.9 to 30:70, more preferably in a rangeof 0.2:99.8 to 20:80, and still more preferably in a range of 0.5:99.5to 10:90.

<Curable Compound>

The composition of the present invention may further include a curablecompound. The curable compound may be a polymerizing compound or anon-polymerizing compound such as a binder. In addition, the curablecompound may be a thermosetting compound or a photocross-linkingcompound and is preferably a thermosetting composition due to its highreaction rate.

<<Compound having polymerizable Group>>

The composition of the present invention may include a compound having apolymerizable group (hereinafter, in some cases, referred to as“polymerizing compound”). A group of such compounds is widely known inthe corresponding industrial field and, in the present invention, thesecompounds can be used without any particular limitation. The compoundsmay have any chemical form of, for example, a monomer, an oligomer, aprepolymer, a polymer, and the like.

<<Polymerizing monomer and polymerizing oligomer>>

The composition of the present invention may include a monomer having apolymerizable group (polymerizing monomer) or an oligomer having apolymerizable group (polymerizing oligomer) (hereinafter, in some cases,the polymerizing monomer and the polymerizing oligomer will becollectively referred to as “the polymerizing monomer and the like”) asthe polymerizing compound.

Examples of the polymerizing monomer and the like include unsaturatedcarboxylic acids (for example, acrylic acid, methacrylic acid, itaconicacid, crotonic acid, isocrotonic acid, maleic acid, and the like),esters thereof, and amides thereof and esters of an unsaturatedcarboxylic acid and an aliphatic polyhydric alcohol compound and amidesof an unsaturated carboxylic acid and an aliphatic polyvalent aminecompound are preferred. In addition, addition reactants of anunsaturated carboxylic acid ester or amide having a nucleophilicsubstituent such as a hydroxyl group, an amino group, or a mercaptogroup and a monofunctional or polyfunctional isocyanate or epoxy,dehydration and condensation reactants of an unsaturated carboxylic acidester or amide and a monofunctional or polyfunctional carboxylic acid,and the like are also preferably used. In addition, addition reactantsof an unsaturated carboxyl ester or an amide having an electrophilicsubstituent such as an isocyanate group or an epoxy group and amonofunctional or polyfunctional alcohol, amine, or thiol and,furthermore, substitution reactants of an unsaturated carboxylic acidester or amide having a desorbable substituent such as a halogen groupor a tosyloxy group and a monofunctional or polyfunctional alcohol,amine, or thiol are also preferred. As additional examples, it is alsopossible to use a group of compounds substituted with an unsaturatedphosphonic acid, a vinyl benzene derivative such as styrene, a vinylether, an aryl ether, or the like instead of the above-describedunsaturated carboxylic acid.

As the specific compounds thereof, the compounds described in Paragraphs“0095” to “0108” in JP2009-288705A can be preferably used even in thepresent invention.

In addition, as the polymerizing monomer and the like, it is possible touse a compound having an ethylenic unsaturated group which has at leastone addition-polymerizing ethylene group and a boiling point of 100° C.or higher at normal pressure, and it is also possible to use amonofunctional (meth)acrylate, a difunctional (meth)acrylate, and a tri-or higher-functional (meth)acrylate (for example, tri- to hexafunctional(meth)acrylate).

Examples thereof include monofunctional acrylates or methacrylates suchas polyethylene glycol mono(meth)acrylate, polypropylene glycolmono(meth)acrylate, and phenoxyethyl (meth)acrylate; and substancesobtained by adding ethylene oxide or propylene oxide to a polyfunctionalalcohol such as polyethylene glycol di(meth)acrylate, trimethylolethanetri(meth)acrylate, neopentyl glycol di(meth)acrylate, pentaerythritoltri(meth)acrylate, pentaerythritol tetra(meth)acrylate,dipentaerythritol penta(meth)acrylate, dipentaerythritolhexa(meth)acrylate, hexanediol(meth)acrylate, trimethylolpropanetri(acryloyloxypropyl)ether, tri(acryloyloxyethyl) isocyanurate,glycerin, or trimethylolethane and then (meth)acrylating the mixture.

The polymerizing compound is preferably ethyleneoxy-denaturedpentaerythritol tetraacrylate (NK ester ATM-35E as a commerciallyavailable product: manufactured by Shin-Nakamura Chemical Co., Ltd.),dipentaerythritol triacrylate (KAYARAD D-330 as a commercially availableproduct; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritoltetraacrylate (KAYARAD D-320 as a commercially available product;manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritolpenta(meth)acrylate (KAYARAD D-310 as a commercially available product;manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritolhexa(meth)acrylate (KAYARAD DPHA as a commercially available product;manufactured by Nippon Kayaku Co., Ltd.), and structures in which theabove-described (meth)acryloyl groups are bonded to each other throughethylene glycol and propylene glycol residues. In addition, the oligomertypes thereof can also be used. It is also possible to use the compoundsdescribed in Paragraphs “0248” to “0251” in JP2007-269779A in thepresent invention.

Examples of the polymerizing monomer and the like include thepolymerizing monomer and the like described in Paragraph “0477” inJP2012-208494A (Paragraph “0585” in the corresponding US2012/0235099A)and the content thereof is incorporated into the specification of thepresent application. In addition, DIGLYCERIN EO (ethyleneoxide)-denatured (meth)acrylate (M-460 as a commercially availableproduct; manufactured by Toagosei Co., Ltd.) can be used.Pentaerythritol tetraacrylate (manufactured by Shin-Nakamura ChemicalCo., Ltd., A-TMMT) and 1,6-hexanediol diacrylate (manufactured by NipponKayaku Co., Ltd., KAYARAD HDDA) can also be used. The oligomer typesthereof can also be used.

Examples thereof include RP-1040 (manufactured by Nippon Kayaku Co.,Ltd.).

In the present invention, as the monomer having an acid group, it ispossible to use an ester of an aliphatic polyhydroxy compound and anunsaturated carboxylic acid which is a polyfunctional monomer providedwith an acid group by reacting an unreacted hydroxyl group in analiphatic polyhydroxy compound and a non-aromatic carboxy anhydride.Examples of commercially available products thereof include ARONIXseries M-305, M-510, M-520, and the like which are polybasicacid-denatured acryl oligomers manufactured by Toagosei Co., Ltd.

The acid value of the polyfunctional monomer having an acid group is ina range of 0.1 mg-KOH/g to 40 mg-KOH/g and particularly preferably in arange of 5 mg-KOH/g to 30 mg-KOH/g. In a case in which two or morepolyfunctional monomers having different acid groups are jointly used orpolyfunctional monomers having no acid groups are jointly used, it isessentially required to prepare the polyfunctional monomers so that allthe acid values of the polyfunctional monomers fall within theabove-described range.

<<Polymer having polymerizable Group in Side Chain>>

The second aspect of the composition of the present invention may be anaspect in which a polymer having a polymerizable group in a side chainis provided as the polymerizing compound. Examples of the polymerizablegroup include an ethylenic unsaturated double-bonded group, an epoxygroup, and an oxetanyl group.

<<Compound having epoxy Group or oxetanyl Group>>

A third aspect of the present invention may be an aspect in which acompound having an epoxy group or an oxetanyl group is included as thepolymerizing compound. Examples of the compound having an epoxy group oran oxetanyl group include polymers having an epoxy group in the sidechain and polymerizing monomers or oligomers having two or more epoxygroups in the molecule and specific examples thereof include bisphenolA-type epoxy resins, bisphenol F-type epoxy resins, phenol novolac-typeepoxy resins, cresol novolac-type epoxy resins, and aliphatic epoxyresins. In addition, examples thereof also include a monofunctional orpolyfunctional glycidyl ether compound.

As the above-described compound, a commercially available product may beused or the compound can be obtained by introducing an epoxy group intothe side chain in the polymer.

Regarding the commercially available product, for example, thedescription of Paragraphs “0191” and the like in JP2012-155288A can bereferred to and the content thereof is incorporated into thespecification of the present application by reference.

Examples of the commercially available product include polyfunctionalaliphatic glycidyl ether compounds such as DENACOL EX-212L, EX-214L,EX-216L, EX-321L, and EX-850L (all manufactured by Nagase ChemteXCorporation). The above-described products are low-chlorine products andEX-212, X-214, EX-216, EX-321, EX-850, and the like, which are notlow-chlorine products, can also be used in a similar manner.

Additionally, examples thereof include ADEKA RESIN EP-4000S, ADEKA RESINEP-4003S, ADEKA RESIN EP-4010S, ADEKA RESIN EP-4011S (all manufacturedby Adeka Corporation), NC-2000, NC-3000, NC-7300, XD-1000, EPPN-501,EPPN-502 (all manufactured by Adeka Corporation), JER1031S, and thelike.

Furthermore, examples of the commercially available product of thephenol novolac-type epoxy resins include JER-157S65, JER-152, JER-154,JER-157S70 (all manufactured by Mitsubishi Chemical Corporation), andthe like.

Specific examples of the polymer having an oxetanyl group in the sidechain and the above-described polymerizing monomer or oligomer havingtwo or more oxetanyl groups in the molecule that can be used includeARON OXETANE OXT-121, OXT-221, OX-SQ, and PNOX (all manufactured byToagosei Co., Ltd.).

In a case in which the compound is synthesized by introducing an epoxygroup into the side chain of the polymer, an epoxy group can beintroduced by causing an introduction reaction in an organic solventusing, for example, a tertiary amine such as triethylamine orbenzylmethylamine, a quaternary ammonium salt such asdodecyltrimethylammonium chloride, tetramethylammonium chloride, ortetraethylammonium chloride, pyridine, triphenylphosphine, or the likeas a catalyst at a reaction temperature in a range of 50° C. to 150° C.for several hours to several tens of hours. The amount of an alicyclicepoxy unsaturated compound introduced can be controlled so that the acidvalue of the obtained polymer falls into a range of 5 KOH.mg/g to 200KOH.mg/g. In addition, the molecular weight can be set in a range of 500to 5000000 and furthermore set in a range of 1000 to 500000 in terms ofweight average.

As the epoxy unsaturated compound, a compound having a glycidyl group asthe epoxy group such as glycidyl (meth)acrylate or allylglycidyl ethercan be used. Regarding the above-described compound, for example, thedescription of Paragraph “0045” of JP2009-265518A can be referred to,and the content thereof is incorporated into the present specificationfor reference.

In the present invention, the composition preferably further includes apolymer having a cross-linking group such as an unsaturated double bond,an epoxy group, or an oxetanyl group at a side chain. In such a case, itis possible to further improve film-forming properties (suppression ofcracking or warping) and humidity resistance when a cured film isproduced. Specific examples of the polymer include the followingpolymers.

The amount of the curable compound added to the composition of thepresent invention can be set in a range of 1% by mass to 50% by mass,more preferably in a range of 1% by mass to 30% by mass, andparticularly preferably in a range of 1% by mass to 10% by mass inrelation to the total solid content excluding the solvent.

The number of the polymerizing compounds may be one or more and, in acase in which two or more polymerizing compounds are used, the totalamount thereof needs to fall into the above-described range.

<Binder polymer>

The present invention may further include a binder polymer as necessaryfor the purpose of improving coating characteristics. As the binderpolymer, an alkali-soluble resin can be used.

Regarding the alkali-soluble resin, the description of Paragraphs “0558”to “0571” and thereafter of JP2012-208494A (“0685” to “0700” in thespecification of the corresponding US2012/0235099A) can be referred to,and the content thereof is incorporated into the present specification.

The content of the binder polymer in the present invention can be set to80 mass % or lower of the total solid content of the composition, andcan also be set to 50 mass % or lower, and furthermore, 30 mass % orlower.

<Surfactant>

The composition of the present invention may include a surfactant. Onlyone surfactant may be used or a combination of two or more surfactantsmay be used. The amount of the surfactant added can be set in a range of0.0001% by mass to 2% by mass of the solid content of the composition ofthe present invention, and can be set in a range of 0.005% by mass to1.0% by mass, and furthermore, in a range of 0.01% by mass to 0.1% bymass.

As the surfactant, a variety of surfactants such as a fluorine-basedsurfactant, a nonionic surfactant, a cationic surfactant, an anionicsurfactant, and a silicone-based surfactant can be used.

Particularly, when the composition of the present invention includes atleast any one of a fluorine-based surfactant and a silicone-basedsurfactant, the liquid characteristics (particularly, fluidity) arefurther improved when a coating fluid is produced, and thus it ispossible to further improve the evenness of the coating thickness orliquid-saving properties.

That is, in a case in which a film is formed using a coating fluid towhich the composition including at least any one of fluorine-basedsurfactants and silicone-based surfactants is applied, the surfacetension between a surface to be coated and the coating fluid decreasesand thus the wetting properties with respect to the surface to be coatedare improved and the coating properties with respect to the surface tobe coated are improved. Therefore, in a case in which a thin film havinga thickness of approximately several micrometers is formed using a smallamount of the fluid as well, the inclusion of the surfactant iseffective since a film having a uniform thickness with little thicknessvariation is more preferably formed.

The content of fluorine in the fluorine-based surfactant can be set, forexample, in a range of 3% by mass to 40% by mass.

Examples of the fluorine-based surfactant include MEGAFACE F171,MEGAFACE F172, MEGAFACE F173, MEGAFACE F176, MEGAFACE F177, MEGAFACEF141, MEGAFACE F 142, MEGAFACE F 143, MEGAFACE F 144, MEGAFACE R30,MEGAFACE F437, MEGAFACE F479, MEGAFACE F482, MEGAFACE F554, MEGAFACEF780, MEGAFACE R08 (manufactured by DIC Corporation), FLUORAD FC430,FLUORAD FC431, FLUORAD FC171 (manufactured by 3M Japan Limited.),SURFLON S-382, SURFLON S-141, SURFLON S-145, SURFLON SC-101, SURFLONSC-103, SURFLON SC-104, SURFLON SC-105, SURFLON SC1068, SURFLON SC-381,SURFLON SC-383, SURFLON 5393, SURFLON KH-40 (all manufactured by AsahiGlass Co., Ltd.), EFTOP EF301, EFTOP EF303, EFTOP EF351, EFTOP EF352(all manufactured by Jemco Co., Ltd.), PF636, PF656, PF6320, PF6520,PF7002 (manufactured by OMNOVA Solution Inc.), and the like.

As the fluorine-based surfactant, a polymer having a fluoroaliphaticgroup can be used. Examples of the polymer having a fluoroaliphaticgroup include a fluorine-based surfactant having a fluoroaliphaticgroup, which is obtained from a fluoroaliphatic compound produced usinga telomerization method (also referred to as a telomer method) or anoligomerization method (also referred to as an oligomer method).

Examples of a commercially available surfactant including a polymerhaving a fluoroaliphatic group in the present invention include thesurfactants described in Paragraph “0552” in JP2012-208494A (“0678” inthe specification of the corresponding US2012/0235099A) and the contentthereof is incorporated into the specification of the presentapplication. In addition, it is possible to use MEGAFACE F-781(manufactured by Dainippon Ink and Chemicals), a copolymer of anacrylate (or methacrylate) having a C₆F₁₃ group, (poly(oxyethylene))acrylate (or methacrylate), and (poly(oxypropylene)) acrylate (ormethacrylate), a copolymer of an acrylate (or methacrylate) having aC₈F₁₇ group and (poly(oxyalkylene)) acrylate (or methacrylate), acopolymer of an acrylate (or methacrylate) having a C₈F₁₇ group,(poly(oxyethylene)) acrylate (or methacrylate), and (poly(oxypropylene))acrylate (or methacrylate), or the like.

Specific examples of nonionic surfactants include the nonionicsurfactants described in Paragraph “0553” (“0679” in the specificationof the corresponding US2012/0235099A) and the like of JP2012-208494A,the content of which is incorporated into the specification of thepresent application.

Examples of the nonionic surfactants include polyoxyethylene alkylethers, polyoxyethylene alkyl allyl ethers, polyoxyethylene fatty acidesters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acidesters, polyoxyethylene alkyl amines, glycerin fatty acid esters,oxyethylene oxypropylene block copolymers, acetylene glycol-basedsurfactants, acetylene-based polyoxyethylene oxides, and the like. Theabove-described surfactants can be used singly or two or moresurfactants can be used.

Examples of specific commercially available products thereof includeSURFYNOL 61, 82, 104, 104E, 104H, 104A, 104BC, 104DPM, 104PA, 104PG-50,104S, 420, 440, 465, 485, 504, CT-111, CT-121, CT-131, CT-136, CT-141,CT-151, CT-171, CT-324, DF-37, DF-58, DF-75, DF-110D, DF-210, GA,OP-340, PSA-204, PSA-216, PSA-336, SE, SE-F, TG, DYNOL 604 (allmanufactured by Nissin Chemical Co., Ltd. and Air Products & Chemicals,Inc.), OLFINE A, B, AK-02, CT-151W, E1004, E1010, P, SPC, STG, Y, 32W,PD-001, PD-002W, PD-003, PD-004, EXP. 4001, EXP. 4036, EXP. 4051,AF-103, AF-104, SK-14, AE-3 (all manufactured by Nissin Chemical Co.,Ltd.), ACETYLENOL BOO, E13T, E40,E60, E81, E100, E200 (all are tradenames and are manufactured by Kawaken Fine Chemicals Co., Ltd.), and thelike. Among these, OLFINE E1010 is preferred.

Specific examples of cationic surfactants include the cationicsurfactants described in Paragraph “0554” in JP2012-208494A (“0680” inthe specification of the corresponding US2012/0235099A) and the contentsthereof can be incorporated into the specification of the presentapplication by reference.

Specific examples of the anionic surfactants include W004, W005, W017(manufactured by Yusho Co., Ltd.), and the like.

Examples of silicone-based surfactants include the silicone-basedsurfactants described in Paragraph “0556” in JP2012-208494A (“0682” inthe specification of the corresponding US2012/0235099A) and the contentsthereof can be incorporated into the specification of the presentapplication by reference. In addition, examples thereof also include“TORAY SILICONE SF8410”, TORAY SILICONE SF8427″, TORAY SILICONE SF8400″,“ST8OPA”, “ST83PA”, “ST86PA” all manufactured by Dow Corning Toray Co.,Ltd., “TSF-400”, “TSF-401”, “TSF-410”, “TSF-4446” manufactured byMomentive Performance Materials Worldwide Inc., “KP321”, “KP323”,“KP324”, “KP340” manufactured by Shin-Etsu Chemical Co., Ltd. and thelike.

<Polymerization Initiator>

The composition of the present invention may include a polymerizationinitiator. The number of the polymerization initiators included may beone or more and, in a case in which the composition includes two or morepolymerization initiators, the total amount thereof falls into theabove-described range. For example, the content of the polymerizationinitiator is preferably in a range of 0.01% by mass to 30% by mass, morepreferably in a range of 0.1% by mass to 20% by mass, and still morepreferably in a range of 0.1% by mass to 15% by mass of the solidcontent of the composition of the present invention.

The polymerization initiator is not particularly limited as long as thepolymerization initiator has the capability of initiating thepolymerization of the polymerizing compounds using either or both lightand heat and can be appropriately selected depending on the purpose, butis preferably a photopolymerizing compound. In a case in whichpolymerization is initiated using light, the polymerization initiatorpreferably has photosensitivity to light rays in an ultraviolet tovisible light range.

In addition, in a case in which polymerization is initiated using heat,a polymerization initiator that is decomposed at a temperature in arange of 150° C. to 250° C. is preferred.

The polymerization initiator that can be used in the present inventionis preferably a compound having at least an aromatic group and examplesthereof include acylphosphine compounds, acetophenone-based compounds,a-aminoketone compounds, benzophenone-based compounds, benzoinether-based compounds, ketal derivative compounds, thioxanthonecompounds, oxime compounds, hexaaryl biimidazole compounds,trihalomethyl compounds, azo compounds, organic peroxides, diazoniumcompounds, iodonium compounds, sulfonium compounds, azinium compounds,ketal derivative compounds, onium salt compounds such as metallocenecompounds, organic boron salt compounds, disulfone compounds, and thelike.

From the viewpoint of sensitivity, oxime compounds, acetophenone-basedcompounds, a-aminoketone compounds, trihalomethyl compounds, hexaarylbiimidazole compounds, and thiol compounds are preferred.

Regarding the acetophenone-based compounds, the trihalomethyl compounds,the hexaaryl biimidazole compounds, and the oxime compounds,specifically, the description in Paragraphs “0506” to “0510” inJP2012-208494A (“0622” to “0628” in the specification of thecorresponding US2012/0235099A) and the like, can be referred to and thecontent thereof is incorporated into the specification of the presentapplication.

The photopolymerization initiator is more preferably a compound selectedfrom a group consisting of an oxime compound, an acetophenone-basedcompound, and an acylphosphine compound. More specifically, for example,it is also possible to use the aminoacetophenone-based initiatorsdescribed in JP 1998-291969A (JP-H10-291969A), the acylphosphineoxide-based initiators described in JP4225898B, the above-describedoxime-based initiators, and, furthermore, as the oxime-based initiators,the compounds described in JP2001-233842A.

As the oxime compound, it is possible to use a commercially availableproduct IRGACURE-OXE01 (manufactured by BASF) or IRGACURE-OXE02(manufactured by BASF). As the acetophenone-based initiator, it ispossible to use commercially available products IRGACURE-907,IRGACURE-369, and IRGACURE-379 (trade name, all manufactured by BASFJapan). In addition, as the acylphosphine-based initiator, it ispossible to use a commercially available product IRGACURE-819 orDAROCUR-TPO (trade name, manufactured by BASF Japan).

<Other Components>

In the composition of the present invention, in addition to theabove-described essential components or the above-described additives,other components can be appropriately selected and used depending on thepurpose as long as the effect of the present invention is not impaired.

Examples of other components that can be jointly used include adispersing agent, a sensitizer, a cross-linking agent, a curingaccelerator, a filler, a thermal curing accelerator, athermopolymerization inhibitor, a plasticizer, and the like and,furthermore, an accelerator of adhesion to the surface of a basematerial and other auxiliary agents (for example, conductive particles,a filler, a defoamer, a flame retardant, a levelling agent, a peelingaccelerator, an antioxidant, a fragrance, a surface tension adjuster, achain transfer agent, and the like) may also be jointly used.

When the composition of the present invention appropriately includes theabove-described components, it is possible to adjust properties such asstability and film properties of a target near-infrared-absorbingfilter.

Regarding the above-described components, for example, the descriptionsin Paragraphs “0183” and thereafter in JP2012-003225A (“0237” andthereafter in the specification of the corresponding US2013/0034812A),Paragraphs “0101” and “0102”, Paragraphs “0103” and “0104”, andParagraphs “0107” to “0109” in JP2008-250074A, and the like can bereferred to and the contents thereof can be incorporated into thespecification of the present application.

The near-infrared-absorbing composition is preferably filtered using afilter for the purpose of removing a foreign substance or reducingdefects. A filter can be used without any particular limitations as longas the filter has been used thus far for filtration use. Examplesthereof include filters made of a fluorine resin such aspolytetrafluoroethylene (PTFE), a polyamide-based resin such as nylon, apolyolefin resin (including a high density and a ultrahigh molecularweight) such as polyethylene or polypropylene (PP), or the like. Amongthese materials, polypropylene (including a high-density polypropylene)and nylon are preferred.

The pore diameter of the filter is preferably in a range ofapproximately 0.1 μm to 7.0 μm, more preferably in a range ofapproximately 0.2 μm to 2.5 μm, still more preferably in a range ofapproximately 0.2 μm to 1.5 μm, and particularly preferably in a rangeof approximately 0.3 μm to 0.7 μm. When the pore diameter thereof iswithin the above-described range, it becomes possible to reliably removefine foreign substances such as impurities or aggregated substancesincluded in the near-infrared-absorbing composition while suppressingfilter clogging.

When the filter is used, different filters may be combined together. Atthis time, the number of times of filtering using a first filter may beone or more. In a case in which filtering is performed multiple timesusing a combination of different filters, the pore diameter of a filterused for the first filtering is preferably identical to or larger thanthe pore diameter of a filter used for the second or later filtering. Inaddition, the first filters having different pore diameters within theabove-described range may be combined together. Regarding the porediameter, the nominal value by a filter maker can be referred to. As acommercially available filter, it is possible to select a filter from,for example, a variety of filters provided by Pall Corporation, ToyoRoshi Kaisha, Ltd., Nihon Entergris K.K. (formerly Mikolis Corporation),Kitz Microfilter Corporation, and the like.

As a second filter, it is possible to use a filter formed using the samematerial as for the above-described first filter. The pore diameter ofthe second filter is preferably in a range of approximately 0.2 μm to10.0 μm, more preferably in a range of approximately 0.2 μm to 7.0 μm,and still more preferably in a range of approximately 0.3 μm to 6.0 μm.When the pore diameter is set in the above-described range, it ispossible to more reliably remove a foreign substance mixed into thenear-infrared-absorbing composition.

Since the composition of the present invention can be produced in aliquid form, a near-infrared cut filter can be easily produced by, forexample, directly applying and drying the composition of the presentinvention, and it is possible to improve production suitability whichhas been insufficient in the above-described near-infrared cut filter ofthe related art.

In the near-infrared cut filter, the light transmittance thereofpreferably satisfies at least one of the following conditions (1) to(9), more preferably satisfies all of the following conditions (1) to(8), and still more preferably satisfies all of the following conditions(1) to (9).

(1) The light transmittance at a wavelength of 400 nm is preferably 80%or higher, more preferably 90% or higher, still more preferably 92% orhigher, and particularly preferably 95% or higher.

(2) The light transmittance at a wavelength of 450 nm is preferably 80%or higher, more preferably 90% or higher, still more preferably 92% orhigher, and particularly preferably 95% or higher.

(3) The light transmittance at a wavelength of 500 nm is preferably 80%or higher, more preferably 90% or higher, still more preferably 92% orhigher, and particularly preferably 95% or higher.

(4) The light transmittance at a wavelength of 550 nm is preferably 80%or higher, more preferably 90% or higher, still more preferably 92% orhigher, and particularly preferably 95% or higher.

(5) The light transmittance at a wavelength of 700 nm is preferably 20%or lower, more preferably 15% or lower, still more preferably 10% orlower, and particularly preferably 5% or lower.

(6) The light transmittance at a wavelength of 750 nm is preferably 20%or lower, more preferably 15% or lower, still more preferably 10% orlower, and particularly preferably 5% or lower.

(7) The light transmittance at a wavelength of 800 nm is preferably 20%or lower, more preferably 15% or lower, still more preferably 10% orlower, and particularly preferably 5% or lower.

(8) The light transmittance at a wavelength of 850 nm is preferably 20%or lower, more preferably 15% or lower, still more preferably 10% orlower, and particularly preferably 5% or lower.

(9) The light transmittance at a wavelength of 900 nm is preferably 20%or lower, more preferably 15% or lower, still more preferably 10% orlower, and particularly preferably 5% or lower.

The film thickness of the near-infrared cut filter is preferably 500 μmor smaller, more preferably 300 μm or smaller, still more preferably 250μm or smaller, and particularly preferably 200 μm. In addition, the filmthickness thereof is preferably 1 μm or greater, more preferably 20 μmor greater, still more preferably 50 μm or greater, and particularlypreferably 100 μm or greater. Particularly, the film thickness thereofis preferably in a range of 1 μm to 500 μm, more preferably in a rangeof 1 μm to 300 μm, and still more preferably in a range of 1 μm to 200μm. In the present invention, even in a case in which a film has a thinthickness as described above, it is possible to maintain highnear-infrared-shielding properties.

In the near-infrared cut filter of the present invention, the percentageof a change in absorbance at a wavelength of 400 nm and the percentageof a change in absorbance at a wavelength of 800 nm before and afterheating of the near-infrared cut filter at 200° C. for five minutes areboth preferably 7% or lower and particularly preferably 5% or lower.

In addition, in the near-infrared cut filter of the present invention,the percentages of a change in the absorbance ratio obtained from thefollowing expression before and after the filter is left to stand forone hour at a high temperature and a high humidity which are 85° C. anda relative humidity of 85% are preferably 7% or lower, more preferably4% or lower, and still more preferably 2% or lower respectively.

Percentage of change in absorbance ratio (%)=[(Absorbance ratio beforetest-absorbance ratio after test)/absorbance ratio before test]×100 (%)

Here, the absorbance ratio refers to (maximum absorbance at a wavelengthin a range of 700 nm to 1400 nm/minimum absorbance at a wavelength in arange of 400 nm to 700 nm).

Examples of the use of the near-infrared-absorbing composition of thepresent invention include a near-infrared cut filter on thelight-receiving side of a solid photographing element (for example, anear-infrared cut filter for a wafer-level lens or the like), anear-infrared cut filter on the rear surface side (the side opposite tothe light-receiving side) of a solid photographing element, and thelike. The near-infrared-absorbing composition of the present inventionis preferably used for a light shielding film on the light-receivingside of a solid photographing element. Particularly, thenear-infrared-absorbing composition of the present invention ispreferably directly applied onto an imaging sensor for a solidphotographing element so as to form a coated film.

In addition, in a case in which an infrared cut layer is formed throughcoating, the viscosity of the near-infrared-absorbing composition of thepresent invention is preferably in a range of 1 mPa·s to 3000 mPa·s,more preferably in a range of 10 mPa·s to 2000 mPa·s, and still morepreferably in a range of 100 mPa·s to 1500 mPa·s.

In a case in which the near-infrared-absorbing composition of thepresent invention is for a near-infrared cut filter on a light-receivingside of a solid photographing element and forms an infrared cut layerthrough coating, from the viewpoint of a property for forming a thickfilm and uniform coatability, the viscosity of thenear-infrared-absorbing composition is preferably in a range of 10 mPa·sto 3000 mPa·s, more preferably in a range of 500 mPa·s to 1500 mPa·s,and still more preferably in a range of 700 mPa·s to 1400 mPa·s.

The total solid content of the near-infrared-absorbing composition ofthe present invention is varied depending on a coating method, but ispreferably 1% by mass or higher of the composition and more preferably10% by mass or higher. Particularly, the total solid content thereof ispreferably in a range of 1% by mass to 50% by mass of the composition,more preferably in a range of 1% by mass to 30% by mass, and still morepreferably in a range of 10% by mass to 30% by mass.

The present invention may be a laminate including a near-infrared cutlayer obtained by hardening the near-infrared-absorbing composition anda dielectric multilayer film. Examples of an aspect of the presentinvention include (i) an aspect in which a transparent support, thenear-infrared cut layer, and the dielectric multilayer film are providedin the above-described order and (ii) an aspect in which thenear-infrared cut layer, a transparent support, and the dielectricmultilayer film are provided in the above-described order. Theabove-described transparent support may be a glass substrate or atransparent resin substrate.

The dielectric multilayer film is a film having a capability ofreflecting and/or absorbing near-infrared rays.

As a material for the dielectric multilayer film, for example, a ceramicmaterial can be used. Alternatively, a noble metal film absorbing lightin the near-infrared range may be used in consideration of thickness andthe number of layers so that the visible light transmittance of thenear-infrared cut filter is not affected.

As the dielectric multilayer film, specifically, a constitution in whichhigh-refractive-index material layers and low-refractive-index materiallayers are alternately laminated can be preferably used.

As a material for constituting the high-refractive-index material layer,a material having a refractive index of 1.7 or higher can be used, and amaterial having a refractive index generally in a range of 1.7 to 2.5 isselected.

Examples of the above-described material include titanium oxide(titania), zirconium oxide, tantalum pentoxide, niobium pentoxide,lanthanum oxide, yttrium oxide, zinc oxide, zinc sulfide, indium oxide,and a material containing the above-described oxide as a main componentand a small amount of titanium oxide, tin oxide, and/or cerium oxide.Among these, titanium oxide (titania) is preferred.

As a material for constituting the low-refractive-index material layer,a material having a refractive index of 1.6 or lower can be used, and amaterial having a refractive index generally in a range of 1.2 to 1.6 isselected.

Examples of the above-described material include silica, alumina,lanthanum fluoride, magnesium fluoride, and sodium aluminumhexafluoride. Among these, silica is preferred.

The thickness of each of the high-refractive-index material layer andthe low-refractive-index material layer is generally a thickness of 0.1λto 0.5λ of the wavelength λ (nm) of an infrared ray to shield. When thethickness is outside the above-described range, the product (nxd) of therefractive index (n) and the film thickness (d) becomes significantlydifferent from the optical film thickness computed from λ/4, and thusthe relationship of optical characteristics such as reflection andrefraction is destroyed, and there is a tendency that the control ofshielding and permeation of a specific wavelength becomes difficult.

In addition, the number of layers laminated in the dielectric multilayerfilm is preferably in a range of 5 to 50 and more preferably in a rangeof 10 to 45.

The near-infrared cut filter is used for a lens (a camera lens in adigital camera, a mobile phone, an in-vehicle camera, or the like or anoptical lens such as a f-O lens or a pickup lens) and an optical filterfor a semiconductor light-receiving element which have a function ofabsorbing and cutting near-infrared rays, a near-infrared-absorbing filmor a near-infrared-absorbing sheet which shields heat rays for energysaving, an agricultural coating agent which aims the selective use ofsunlight, a recording medium which uses near-infrared-absorbing heat, anear-infrared filter for an electronic device or a photograph,protective glasses, sunglasses, a heat ray shielding film, an opticalletter-reading record, the prevention of copying a confidentialdocument, an electrophotographic photoreceptor, laser fusion, and thelike. In addition, the near-infrared cut filter is also useful for anoise cut filter for a CCD camera and a filter for a CMOS image sensor.

<Process for Producing Near-Infrared Cut Filter>

A process for producing a near-infrared cut filter of the presentinvention preferably includes a step of applying thenear-infrared-absorbing composition of the present invention onto a basematerial and a step of drying the near-infrared-absorbing compositionapplied onto the base material.

Examples of the method for applying the near-infrared-absorbingcomposition of the present invention onto a base material includedropwise addition, immersion, coating, and printing. Specifically, themethod is preferably selected from drop casting, applicator application,dip coating, slit coating, screen printing, spray coating, and spincoating.

In the case of the dropwise addition method (drop casting), it ispreferable to form a dropwise addition region for thenear-infrared-absorbing composition including a photoresist as apartition wall on a support so that a uniform film can be obtained witha predetermined film thickness. A desired film thickness can be obtainedby adjusting the amount of the near-infrared-absorbing composition addeddropwise, the concentration of the solid content, and the area of thedropwise addition region to be desired values. The thickness of thedried film is not particularly limited and can be appropriately selecteddepending on the purposes.

A support may be a transparent substrate made of glass or the like, asolid photographing element, another substrate (for example, a glasssubstrate 30 described below) provided on the light-receiving side ofthe solid photographing element, or a layer such as a flattened layerprovided on the light-receiving side of the solid photographing element.

In addition, the conditions for drying the coated film vary depending onthe kind and proportions of individual components and a solvent;however, generally, the coated film is dried at a temperature in a rangeof 60° C. to 200° C. for approximately 30 seconds to 15 minutes.

A method for foiming a near-infrared cut filter using thenear-infrared-absorbing composition of the present invention may includeother steps. The other steps are not particularly limited and can beappropriately selected depending on the purpose. Examples thereofinclude a surface treatment step of the base material, a pretreatmentstep (prebaking step), a curing treatment step, a post heating step(post baking step), and the like.

<Preheating step and post heating step>The heating temperatures in thepreheating step and the post heating step are generally in a range of80° C. to 200° C. and preferably in a range of 90° C. to 180° C.

The heating times in the preheating step and the post heating step aregenerally in a range of 30 seconds to 400 seconds and preferably in arange of 60 seconds to 300 seconds.

<Curing Treatment Step>

The curing treatment step refers to a step of carrying out a curingtreatment on the formed film as necessary and the curing treatmentimproves the mechanical strength of the near-infrared cut filter.

The curing treatment step is not particularly limited and can beappropriately selected depending on the purpose and preferred examplesthereof include a full-surface exposure treatment, a full-surfacethermal treatment, and the like. In the present invention, the meaningof “exposure” includes the irradiation of the surface with radioactiverays such as electron beams or X rays as well as light rays having avariety of wavelengths.

The exposure is preferably carried out through irradiation withradioactive rays and, as the radioactive rays that can be used in theexposure, particularly, ultraviolet rays such as electron beams, KrF,ArF, g-rays, h-rays, or i-rays or visible light are preferably used.Preferably, KrF, g-rays, h-rays, or i-rays are preferred.

Examples of the exposure method include stepper exposure, exposure usinga high-pressure mercury lamp, and the like.

The exposure amount is preferably in a range of 5 J/cm² to 3000 mJ/cm²,more preferably in a range of 10 J/cm² to 2000 mJ/cm², and particularlypreferably in a range of 50 J/cm² to 1000 mJ/cm².

Examples of a method for the full-surface exposure treatment include amethod in which the full surface of the above-described formed film isexposed. In a case in which the near-infrared-absorbing compositionincludes the polymerizing compound, the full-surface exposureaccelerates the curing of a polymerizing component in the film formed ofthe composition, makes the film cured to a greater extent, and improvesthe mechanical strength and the durability.

An apparatus for carrying out the full-surface exposure is notparticularly limited and can be appropriately selected depending on thepurpose, and preferred examples thereof include UV steppers such asultrahigh-pressure mercury lamps.

In addition, examples of the method for the full-surface thermaltreatment include a method in which the full surface of theabove-described formed film is heated. The heating of the full surfaceincreases the film strength of a pattern.

The heating temperature during the full-surface heating is preferably ina range of 120° C. to 250° C. When the heating temperature is 120° C. orhigher, the film strength is improved by the heating treatment and, whenthe heating temperature is 250° C. or lower, components in the film aredecomposed and it is possible to prevent the film from becoming weak andbrittle.

The heating time in the full-surface heating is preferably in a range of3 minutes to 180 minutes and more preferably in a range of 5 minutes to120 minutes.

An apparatus for carrying out the full-surface heating is notparticularly limited and can be appropriately selected from well-knownapparatuses depending on the purpose, and examples thereof include adrying oven, a hot plate, an IR heater, and the like.

<Camera Module and Process for Producing Camera Module>

In addition, the present invention also relates to a camera modulehaving a solid photographing element and a near-infrared cut filterdisposed on the light-receiving side of the solid photographing element,in which the near-infrared cut filter is the near-infrared cut filter ofthe present invention.

Hereinafter, a camera module according to an embodiment of the presentinvention will be described with reference to FIGS. 3 and 4, but thepresent invention is not limited to the following specific example.

Meanwhile, in FIGS. 3 and 4, common reference signs will be given tocommon portions.

In addition, in the description, “up”, “upward”, and “upside” indicate aside far from a silicon substrate 10, and “down”, “downward”, and“downside” indicate a side close to the silicon substrate 10.

FIG. 3 is a schematic sectional view illustrating the constitution of acamera module including a solid photographing element.

A camera module 200 illustrated in FIG. 3 is connected to a circuitboard 70, which is a mounting substrate, through solder balls 60 whichis a connection member.

In detail, the camera module 200 includes a solid photographing element(solid photographing element substrate) 100 including photodiodes on afirst main surface of the silicon substrate, a flattening layer (notillustrated in FIG. 3) provided on the first main surface side(light-receiving side) of the solid photographing element 100, anear-infrared cut filter 42 provided on the flattening layer, a lensholder 50 which is disposed above the near-infrared cut filter 42 andincludes an imaging lens 40 in an inner space, and a light andelectromagnetic shield 44 disposed so as to cover the surrounding of thesolid photographing element 100 and the glass substrate 30. Meanwhile,the glass substrate 30 (light-permeable substrate) may be provided onthe flattening layer. The respective members are adhered together usingan adhesive 45.

The present invention relates to a process of producing a camera moduleincluding the solid photographing element 100 and the near-infrared cutfilter 42 disposed on the light-receiving side of the solidphotographing element, including a step of forming the near-infrared cutfilter 42 by applying the near-infrared-absorbing composition of thepresent invention to the light-receiving side of the solid photographingelement. In the camera module according to the present embodiment, thenear-infrared cut filter 42 can be formed on the flattening layer by,for example, applying (for example, coating) the near-infrared-absorbingcomposition of the present invention. The method for applying thenear-infrared-absorbing composition onto the base material is asdescribed above.

In the camera module 200, incidence ray hu from the outside sequentiallypermeates the imaging lens 40, the near-infrared cut filter 42, theglass substrate 30, and the flattening layer, and then reaches theimaging element portion in the solid photographing element 100.

The camera module 200 includes the near-infrared cut filter directlyprovided on the flattening layer, but the near-infrared cut filter maybe directly provided on a micro lens without the flattening layer, orthe near-infrared cut filter may be provided on the glass substrate 30,or the glass substrate 30 provided with the near-infrared cut filter maybe adhered to the camera module.

FIG. 4 is an enlarged sectional view of the solid photographing element100 in FIG. 3.

The solid photographing element 100 includes the imaging elementportions 12 on the first main surface of the silicon substrate 10, whichis a substrate, an interlayer insulating film 13, a base layer 14, acolor filter 15, an overcoat 16, and micro lenses 17 in this order. Ared color filter 15R, a green color filter 15G, and a blue color filter15B (hereinafter, these will be collectively referred to as “colorfilter 15”) or the micro lenses 17 are respectively disposed so as tocorrespond to the imaging element portions 12. A light shielding film18, an insulating film 22, a metallic electrode 23, a solder resistlayer 24, an inner electrode 26, and an element surface electrode 27 areprovided on a second main surface which is on a side opposite to thefirst main surface of the silicon substrate 10. The respective membersare adhered together using an adhesive 20.

A flattening layer 46 and the near-infrared cut filter 42 are providedon the micro lenses 17. The near-infrared cut filter 42 may be providedon the micro lenses 17 and between the base layer 14 and the colorfilter 15 or between the color filter 15 and the overcoat 16 instead ofbeing provided on the flattening layer 46. Particularly, thenear-infrared cut filter is preferably provided at a position 2 mm orless (more preferably 1 mm or less) away from the surfaces of the microlenses 17. When the near-infrared cut filter is provided at thisposition, it is possible to simplify the step of forming thenear-infrared cut filter and to sufficiently cut unnecessarynear-infrared rays travelling toward the micro lenses, and thus thenear-infrared-shielding properties can be further enhanced.

Regarding the solid photographing element 100, the description ofParagraph “0245” (Paragraph “0407” in the specification of thecorresponding US2012/068292A) of JP2012-068418A can be referred to, andthe content thereof is incorporated into the present specification.

The near-infrared cut filter can be subjected to a solder reflow step.When the camera module is produced through the solder reflow step, theautomatic mounting of an electronic component-mounted substrate or thelike which requires soldering becomes possible, and it is possible tosignificantly improve the productivity compared with a case in which thesolder reflow step is not used. Furthermore, since the solder reflowstep is automatically carried out, it is also possible to reduce thecost. In a case in which the near-infrared cut filter is subjected tothe solder reflow step, the near-infrared cut filter is exposed to atemperature in a range of approximately 250° C. to 270° C., and thus thenear-infrared cut filter is preferably heat-resistant enough towithstand the solder reflow step (hereinafter, also referred to as“solder reflowability”).

In the present specification, “having solder reflowability” means thatthe near-infrared cut filter maintains its characteristics before andafter being heated at 200° C. for 10 minutes. More preferably, theinfrared cut filter maintains its characteristics before and after beingheated at 230° C. for 10 minutes. Still more preferably, the infraredcut filter maintains its characteristics before and after being heatedat 250° C. for three minutes. In a case in which the near-infrared cutfilter does not have solder reflowability, when being held under theabove-described conditions, there are cases in which thenear-infrared-absorbing function of the near-infrared cut filterdegrades or the functions become insufficient for films.

In addition, the present invention also relates to a process forproducing a camera module including a step of a reflow treatment. Evenwhen the reflow step is provided, the near-infrared cut filter iscapable of maintaining its near-infrared-absorbing function, and thereare no cases in which the characteristics of the camera module havingreduced size and weight and having improved performance are impaired.

FIGS. 5 to 7 are schematic sectional views illustrating examples of aperiphery of a near-infrared cut filter in the camera module.

As illustrated in FIG. 5, the camera module may have the solidphotographing element 100, the flattening layer 46, an ultraviolet andinfrared light-reflecting film 80, a transparent base material 81, anear-infrared-absorbing layer 82, and an antireflection layer 83 in thisorder.

The ultraviolet and infrared light-reflecting film 80 has an effect ofimparting and enhancing the functions of the near-infrared cut filter,and, for example, Paragraphs “0033” to “0039” in JP2013-68688A can bereferred to, and the content thereof is incorporated into the presentspecification.

The transparent base material 81 transmits light having wavelengths inthe visible light range, and, for example, Paragraphs “0026” to “0032”in JP2013-68688A can be referred to, and the content thereof isincorporated into the present specification.

The near-infrared-absorbing layer 82 is a layer formed by applying theabove-described near-infrared-absorbing composition of the presentinvention.

The antireflection layer 83 has a function of preventing the reflectionof light incident on the near-infrared cut filter so as to improve thetransmittance and allowing efficient use of the incidence ray, and, forexample, Paragraph “0040” in JP2013-68688A can be referred to, and thecontent thereof is incorporated into the present specification.

As illustrated in FIG. 6, the camera module may have the solidphotographing element 100, the near-infrared-absorbing layer 82, theantireflection layer 83, the flattening layer 46, the antireflectionlayer 83, the transparent base material 81, and the ultraviolet andinfrared light-reflecting film 80 in this order.

As illustrated in FIG. 7, the camera module may have the solidphotographing element 100, the near-infrared-absorbing layer 82, theultraviolet and infrared light-reflecting film 80, the flattening layer46, the antireflection layer 83, the transparent base material 81, andthe antireflection layer 83 in this order.

Thus far, the embodiment of the camera module has been described withreference to FIGS. 3 to 7, but the embodiment is not limited to theembodiment of FIGS. 3 to 7.

EXAMPLES

Hereinafter, the present invention will be more specifically describedusing examples. Materials, amounts used, proportions, the contents oftreatments, the orders of treatments, and the like described in thefollowing examples can be appropriately changed within the scope of thegist of the present invention. Therefore, the scope of the presentinvention is not limited to specific examples described below.

Synthesis Example 1 synthesis of Near-Infrared-Absorbing Compound A-1

1,3-Propane disulfonic acid (55.1% by mass aqueous solution) (10 partsby mass), water (11.27 parts by mass), and furthermore, copper (II)hydroxide (2.63 parts by mass) were added to and stirred in an eggplantflask and were reacted with each other at 50° C. for one hour. After thereaction, the mixture was cooled to room temperature and was dilutedusing water, thereby obtaining a 25% by mass aqueous solution of anear-infrared-absorbing compound (A-1).

Synthesis Examples 2 to 10 Syntheses of Near-Infrared-AbsorbingCompounds A-2 to A-10

25% by mass aqueous solutions of near-infrared-absorbing compounds (A-2to A-10) were obtained in the same manner as in Synthesis Example 1except for the fact that the kinds of acidic compounds used and theratios between the coordination site equivalent (acid group equivalent)and the copper atom equivalent were changed as shown in Table 20 below.

Synthesis Example 11 Synthesis of Near-Infrared-Absorbing Compound A-11

25% by mass aqueous solution of a near-infrared-absorbing compound A-11was obtained in the same manner as in Synthesis Example 1 except for thefact that a compound (L-1) below was used instead of 1,3-propanedisulfonic acid in Synthesis Example 1. Meanwhile, the ratio(coordination site equivalent/copper atom equivalent) between theequivalent of all coordination sites in the compound (L-1) and theequivalent of copper atoms in copper acetate was 2:1.

Synthesis Example 12 Synthesis of Near-Infrared-Absorbing Compound A-12

A 25% by mass aqueous solution of a near-infrared-absorbing compoundA-12 was obtained in the same manner as in Synthesis Example 1 exceptfor the fact that a compound (L-2) below was used instead of 1,3-propanedisulfonic acid and copper methane sulfonate was used instead of copper(II) hydroxide in Synthesis Example 1. Meanwhile, the ratio(coordination site equivalent/copper atom equivalent) between theequivalent of all coordination sites in the compound (L-2) and theequivalent of copper atoms in copper acetate was 1:1.

Synthesis Example 13 Synthesis of Near-Infrared-Absorbing Compound A-13

A 25% by mass aqueous solution of a near-infrared-absorbing compoundA-13 was obtained in the same manner as in Synthesis Example 1 exceptfor the fact that a compound (L-3) below was used instead of 1,3-propanedisulfonic acid and copper acetate was used instead of copper (II)hydroxide in Synthesis Example 1. Meanwhile, the ratio (coordinationsite equivalent/copper atom equivalent) between the equivalent of allcoordination sites in the compound (L-3) and the equivalent of copperatoms in copper acetate was 2:1.

TABLE 20 Content proportion Coordination site of copper inNear-infrared- equivalent/copper solid contents absorbing compoundLow-molecular-weight compound used atom equivalent (% by mass) A-1

2.0/1.0 23.9 A-2

2.0/1.0 22.7 A-3

2.0/1.0 25.2 A-4

2.0/1.0 16.9 A-5

2.0/1.0 18.2 A-6

2.0/1.0 14.4 A-7

2.0/1.0 20.7 A-8

2.0/1.0 12.3 A-9

2.0/1.0 12.9  A-10

2.0/0.7 20.7

Synthesis Example 14 Synthesis of Near-Infrared-Absorbing Compound B-1

Water (60 parts by mass) was put into a three-neck flask and was heatedto 57° C. in a nitrogen atmosphere. A monomer solution (dropwiseaddition solution A) obtained by dissolving2-acrylamide-2-methylpropanesulfonic acid (100 parts by mass) in water(160 parts by mass) and an initiator solution (dropwise additionsolution B) obtained by dissolving VA-046B (water-soluble azo-basedpolymerization initiator, manufactured by Wako Pure Chemical Industries,Ltd., 1.164 parts by mass) in water (80 parts by mass) were prepared,the dropwise addition solution A and the dropwise addition solution Bwere added dropwise to water at the same time over two hours and werereacted with each other. After being reacted for two hours from thedropwise addition, the dropwise addition solution A and the dropwiseaddition solution B were heated to 65° C. and thus were further reactedwith each other for two hours, thereby obtaining a 25% by mass aqueoussolution of a polymer (P-1). The weight-average molecular weight was100,000.

0.4 equivalents of copper (II) hydroxide (18.83 parts by mass) of theamount of an acid group in (P-1) was added to the obtained (P-1)solution, was stirred together at 50° C. for one hour, and then wasdiluted using water, thereby obtaining a 25% by mass aqueous solution ofa near-infrared-absorbing compound (B-1).

Synthesis Examples 15 to 23 Ssyntheses of Near-Infrared-AbsorbingCompounds B-2 to B-9

Aqueous solutions of near-infrared-absorbing compounds (B-2 to B-9) (B-2to B-5 and B-7 to B-9 were 25% by mass aqueous solutions, and B-6 was a20% by mass aqueous solution) were obtained in the same manner as inSynthesis Example 14 except for the fact that the kinds of polymers usedand the ratios between the coordination site equivalent (acid groupequivalent) and the copper atom equivalent were changed as shown inTable 21 below.

Synthesis Example 24

<<Synthesis of polymer (P-24)>>

1-Methoxy-2-propanol (21 g) was put into a three-neck flask and washeated to 85° C. in a nitrogen atmosphere. Next, a solution obtained bydissolving 2-[2-(3,5-dimethyl-1H-pyrazoryl)]ethylmethacrylate (11.21 g),benzyl methacrylate (18.79 g), and V-601 (azo-based polymerizationinitiator manufactured by Wako Pure Chemical Industries, Ltd., 1.06 g)in 1-methoxy-2-propanol (49 g) was added dropwise thereto over twohours.

After the end of the dropwise addition, the components were stirredtogether for four hours, and a reaction was finished, thereby obtaininga polymer (P-24) below. The weight-average molecular weight of thepolymer (P-24) was 20,000.

<<Synthesis of Near-Infrared-Absorbing Compound B-10>>

2,6-Pyridinedicarboxylic acid (17.82 g) and methanol (50 g) were putinto an eggplant flask and were dissolved at room temperature. Asolution obtained by dissolving copper acetate (19.37 g) in methanol (50g) and water (20 g) was added thereto and was stirred at roomtemperature for 30 minutes, whereby generation of precipitation wasconfirmed. A 1-methoxy-2-propanol solution (100 g, 30% by mass) of thepolymer (P-24) was added thereto and was stirred at room temperature forone hour, thereby obtaining a near-infrared-absorbing composition(B-10). Meanwhile, the ratio (coordination site equivalent/copper atomequivalent) between the equivalent of all coordination sites in thecompound (P-24) and the equivalent of copper atoms in copper acetate was2:1.

Synthesis Example 25 Near-Infrared-Absorbing Compound C-1

Methanesulfonic acid (24.8 parts by mass), water (100 parts by mass),and furthermore, copper (II) hydroxide (25.2 parts by mass) were addedto an eggplant flask, stirred together, and were reacted with each otherat 50° C. for one hour. After the reaction, the mixture was cooled toroom temperature and was diluted using water, thereby obtaining a 25% bymass aqueous solution of a near-infrared-absorbing compound C-1.

TABLE 21 Content proportion Near-infrared- Coordination site of copperin absorbing equivalent/copper solid contents compound Polymer used atomequivalent (% by mass) B-1

2.0/0.8  11.0 B-2

2.0/0.75 18.2 B-3

2.0/0.8  12.2 B-4

2.0/0.90 10.8 B-5

2.0/0.85 11.0 B-6 20% Nation ® Dispersion Solution 2.0/0.95  3.1 DE1021CS type (manufactured by Wako Pure Chemical Industries, Ltd.) B-7

2.0/0.95  8.3 B-8

2.0/0.95 13.3 B-9

2.0/0.85 12.0 C-1 H₃C—SO₃H 2.0/1.0  25.0

<Preparation of Near-Infrared-Absorbing Composition>

An aqueous solution of a near-infrared-absorbing compound was mixed inat mass ratios shown in Table 22, thereby preparingnear-infrared-absorbing compositions 1 to 23 of Examples 1 to 32.

A near-infrared-absorbing composition 21 was prepared by stirring acompound A-11 (10 parts by mass), a compound B-1 (10 parts by mass), andwater (83 parts by mass) at 50° C. for 12 hours. Anear-infrared-absorbing composition 22 was prepared by stirring acompound A-12 (10 parts by mass), a compound B-8 (10 parts by mass), andwater (83 parts by mass) at 50° C. for 12 hours. Anear-infrared-absorbing composition 23 was prepared by stirring acompound A-13 (10 parts by mass), a compound B-10 (10 parts by mass),propylene glycol monomethyl ether (80 parts by mass), and water (3 partsby mass) at 50° C. for 12 hours.

TABLE 22 Near-infrared- Near-infrared- Near-infrared- Near- absorbingabsorbing absorbing Content infrared- compound (A) compound (B) compound(C) A/B/C of copper absorbing (low-molecular- (high-molecular-(low-molecular- (mass (% by composition weight type) weight type) weighttype) ratio) mass) Composition 1 A-8 — — 100/0/0 12.3 Composition 2 A-9— — 100/0/0 12.9 Composition 3 A-3 B-1 — 25/75/0 14.5 Composition 4 A-1B-2 — 5/95/0 18.5 Composition 5 A-2 B-3 — 20/80/0 14.3 Composition 6 A-2B-4 C-1 15/85/0 15.1 Composition 7 A-1 B-5 — 25/75/0 14.2 Composition 8A-8/A-3 B-6 C-1 35/40/25 14.1 (5/5) Composition 9 A-1 B-7 — 35/65/0 13.8Composition 10 A-4 B-7 C-1 10/60/30 14.2 Composition 11 A-7 B-7 C-130/55/15 14.5 Composition 12 A-9/A-3 B-7 — 40/60/0 14.1 (2/8)Composition 13 A-10 B-7 — 50/50/0 14.5 Composition 14 A-2 B-8 — 10/90/014.3 Composition 15 A-5 B-8 — 20/80/0 14.3 Composition 16 A-8 B-8 —5/95/0 13.3 Composition 17 A-10 B-8 — 15/85/0 14.4 Composition 18 A-6B-8 C-1 10/80/10 14.6 Composition 19 A-3 B-9 — 15/85/0 14.0 Composition20 A-6/A-1 B-9 — 25/75/0 14.0 (4/6) Composition 21 A-11 B-1 — 50/50/012.2 Composition 22 A-12 B-8 — 50/50/0 12.2 Composition 23 A-13 B-10 —50/50/0 9.58

<<Production of Near-Infrared Cut Filter>>

Each of the near-infrared-absorbing compositions was coated on a glasssubstrate using dope casting (dropwise addition method), was heated on ahot plate in a stepwise manner of at 60° C. for 10 minutes, at 80° C.for 10 minutes, at 100° C. for 10 minutes, at 120° C. for 10 minutes,and at 140° C. for 10 minutes, thereby producing 100 μm-thicknear-infrared cut filters.

<Evaluation of Near-Infrared-Absorbing Composition>

<<Evaluation of Near-Infrared-Shielding Properties>>

The transmittances at a wavelength of 800 nm of the near-infrared cutfilters obtained as described above were measured using aspectrophotometer U-4100 (manufactured by Hitachi High-TechnologiesCorporation). The near-infrared-shielding properties were evaluatedusing the following standards.

A: Transmittance at 800 nm≦5%

B: 5%<Transmittance at 800 nm≦7%

C: 7%<Transmittance at 800 nm≦10%

D: 10%<Transmittance at 800 nm

<<Evaluation of Heat Resistance 1>>

The near-infrared cut filters obtained as described above were left tostand at 200° C. for five minutes. The maximum absorbance (Absλmax) at awavelength in a range of 700 nm to 1400 nm and the minimum absorbance(Absλmin) at a wavelength in a range of 400 nm to 700 nm of each of thenear-infrared cut filters were measured using a spectrophotometer U-4100(manufactured by Hitachi High-Technologies Corporation) respectivelybefore and after a heat resistance test, and the absorbance ratiorepresented by “Absλmax/Absλmin” was obtained. The percentage of achange in the absorbance ratio represented by |((absorbance ratio beforetest-absorbance ratio after test)/absorbance ratio before test)×100|(%)was evaluated using the following standards. The results are shown inthe following table.

A: Percentage of change in absorbance ratio≦2%

B: 2%<Percentage of change in absorbance ratio≦4%

C: 4%<Percentage of change in absorbance ratio≦7%

D: 7%<Percentage of change in absorbance ratio

<<Evaluation of Heat Resistance 2>>

Heat resistance was evaluated in the same manner as in the evaluation ofheat resistance 1 except for the fact that the heating temperature waschanged from 200° C. to 245° C.

TABLE 23 Near-infrared- Evaluation of heat Composition used shieldingproperties resistance 1 Example 1 Composition 1 B B Example 2Composition 2 B B Example 3 Composition 3 A A Example 4 Composition 4 AB Example 5 Composition 5 A B Example 6 Composition 6 A A Example 7Composition 7 A B Example 8 Composition 8 A A Example 9 Composition 9 AA Example 10 Composition 10 A A Example 11 Composition 11 A A Example 12Composition 12 A A Example 13 Composition 13 A A Example 14 Composition14 A A Example 15 Composition 15 A A Example 16 Composition 16 A AExample 17 Composition 17 A A Example 18 Composition 18 A A Example 19Composition 19 A A Example 20 Composition 20 A A Example 33 Composition21 A A Example 34 Composition 22 A A Example 35 Composition 23 A AEvaluation of heat Composition used resistance 2 Example 21 Composition9 A Example 22 Composition 10 A Example 23 Composition 11 A Example 24Composition 12 A Example 25 Composition 13 A Example 26 Composition 14 AExample 27 Composition 15 A Example 28 Composition 16 A Example 29Composition 17 A Example 30 Composition 18 A Example 31 Composition 19 AExample 32 Composition 20 A

As is clear from Table 23, it was found that the near-infrared-absorbingcomposition of the present invention was capable of maintainingextremely high near-infrared-shielding properties when a cured film wasproduced. In addition, it was found that the near-infrared-absorbingcomposition of the present invention was also favorable in terms of heatresistance.

Particularly, it was found that, in a case in which a copper complex ofan aromatic group-containing polymer was used as thenear-infrared-absorbing compound (B: high-molecular-weight type), heatresistance was more favorable when a cured film was produced.

Even in a case in which a near-infrared cut filter was produced asdescribed below using any one of the near-infrared-absorbingcompositions 1 to 23, near-infrared cut filters can be similarlyproduced. A photoresist was applied onto a glass substrate, and apattern was formed using lithography so as to form partition walls forthe photoresist, thereby forming a dropwise addition region (2 cm×2 cm)for the near-infrared-absorbing composition. Eachnear-infrared-absorbing composition (200 μL) was added dropwise to thedropwise addition region, dried at 40° C. for one hour, and furthermore,the near-infrared-absorbing composition (200 μL) was added dropwisethereto, dried at 40° C. for one hour, and dried at 60° C. for one hour.After that, the near-infrared-absorbing composition was left to standfor 24 hours so as to be dried. The film thickness of the dried coatedfilm was evaluated to be 200 μm. Meanwhile, even when the dropwiseaddition region was produced using Kapton tape as the partition wall, anear-infrared cut filter could be similarly produced.

In the near-infrared-absorbing composition 23 used in Example 35, evenin a case in which propylene glycol monomethyl ether was changed to theequivalent amount of cyclopentanone, the same effects can be obtained.

In addition, even in a case in which filtration is carried out using aDFA4201NXEY (0.45 μm nylon filter) after the preparation of thenear-infrared-absorbing compositions 1 to 23, the same effects can beobtained.

EXPLANATION OF REFERENCES

1A, 1B: near-infrared-absorbing composition

2: copper ion

3: main chain having compound represented by Formula (II)

4: side chain having compound represented by Formula (II)

5: site at which copper is coordinated

6: monovalent group in compound represented by Formula (I)

7: monovalent group in compound represented by Formula (III)

8: site at which cross-linking group is crosslinked

10: silicon substrate

12: imaging element portion

13: interlayer insulating film

14: base layer

15: color filter

16: overcoat

17: micro lens

18: light shielding film

20: adhesive

22: insulating film

23: metallic electrode

24: solder resist layer

26: inner electrode

27: element surface electrode

30: glass substrate

40: imaging lens

42: near-infrared cut filter

44: light and electromagnetic shield

45: adhesive

46: flattening layer

50: lens holder

60: solder ball

70: circuit board

80: ultraviolet and infrared light-reflecting film

81: transparent base material

82: near-infrared-absorbing layer

83: antireflection layer

100: solid photographing element

What is claimed is:
 1. A near-infrared-absorbing composition comprising:a near-infrared-absorbing compound (A1) obtained from a reaction betweena low-molecular-weight compound which has two or more coordination sitesto a metal component or a coordination site to a metal component and across-linking group and has a molecular weight of 1800 or lower or asalt thereof and the metal component; and a near-infrared-absorbingcompound (B) obtained from a reaction between a high-molecular-weightcompound having a repeating unit represented by Formula (II) below or asalt thereof and a metal component:

in Formula (II), R² represents an organic group, Y¹ represents a singlebond or a divalent linking group, and X² represents the coordinationsite to the metal component.
 2. A near-infrared-absorbing compositioncomprising: a near-infrared-absorbing compound obtained from a reactionbetween a low-molecular-weight compound which has two or morecoordination sites to a metal component or a coordination site to ametal component and a cross-linking group and has a molecular weight of1800 or lower or a salt thereof, a high-molecular-weight compound havinga repeating unit represented by Formula (II) below or a salt thereof,and a metal component:

in Formula (II), R² represents an organic group, Y¹ represents a singlebond or a divalent linking group, and X² represents the coordinationsite to the metal component.
 3. The near-infrared-absorbing compositionaccording to claim 1, wherein the low-molecular-weight compound is acompound represented by Formula (I) below:R¹(—X¹)_(n1)   (I) in Formula (I), R¹ represents an nl-valent group, X¹represents the coordination site to the metal component, and n1represents an integer from 2 to
 6. 4. The near-infrared-absorbingcomposition according to claim 1, wherein the low-molecular-weightcompound is a compound represented by Formula (a1-i) below:R¹⁰⁰-L¹⁰⁰-(X¹⁰⁰)_(n)   (a1-i) in Formula (a1-i), X¹⁰⁰ represents thecoordination site to the metal component, n represents an integer from 1to 6, L¹⁰⁰ represents a single bond or a linking group, and R¹⁰⁰represents a cross-linking group.
 5. The near-infrared-absorbingcomposition according to claim 1, wherein a weight-average molecularweight of the high-molecular-weight compound having the repeating unitrepresented by Formula (II) or a salt thereof is in a range of 2,000 to2,000,000.
 6. A near-infrared-absorbing composition comprising: anear-infrared-absorbing compound (A2) obtained from a reaction between alow-molecular-weight compound having a molecular weight of 1800 or lowerwhich is represented by Formula (III) below or a salt thereof and ametal component:R³(—X¹)_(n2)   (III) in Formula (III), R³ represents an n2-valent group,X¹ represents a coordination site to the metal component, and n2represents an integer from 3 to
 6. 7. The near-infrared-absorbingcomposition according to claim 1, wherein the metal component is acopper component.
 8. The near-infrared-absorbing composition accordingto claim 1, wherein the coordination site to the metal component is anacid group.
 9. The near-infrared-absorbing composition according toclaim 1, comprising: a near-infrared-absorbing compound (C) having apartial structure represented by Formula (IV) below:

in Formula (IV), R⁴ represents an organic group, R⁵ represents adivalent group, Y² represents a single bond or a divalent linking group,each of X³ and X⁴ independently represents a site at which a coordinatebond is formed with copper, and Cu represents a copper ion.
 10. Thenear-infrared-absorbing composition according to claim 9, wherein thesite at which a coordinate bond is formed with copper is an acid groupion site derived from an acid group.
 11. The near-infrared-absorbingcomposition according to claim 1, wherein a content of copper in thenear-infrared-absorbing composition is in a range of 2% by mass to 50%by mass of a total amount of solid contents in thenear-infrared-absorbing composition.
 12. The near-infrared-absorbingcomposition according to claim 1, further comprising: an organicsolvent.
 13. The near-infrared-absorbing composition according to claim1, wherein the low-molecular-weight compound forms a structure whichcrosslinks side chains of the high-molecular-weight compound through ametal ion in the metal component.
 14. The near-infrared-absorbingcomposition according to claim 1, wherein the mass ratio between thenear-infrared-absorbing compound (A1) and the near-infrared-absorbingcompound (B) is in a range of 3:97 to 70:30.
 15. A near-infrared cutfilter obtained using the near-infrared-absorbing composition accordingto claim
 1. 16. The near-infrared cut filter according to claim 15,wherein a percentage of a change in absorbance at a wavelength of 400 nmand a percentage of a change in absorbance at a wavelength of 800 nmbefore and after heating of the near-infrared cut filter at 200° C. forfive minutes are both 7% or lower.
 17. A process for producing anear-infrared cut filter, comprising: forming a near-infrared cut filterby applying the near-infrared-absorbing composition according to claim 1to a light-receiving side of a solid photographing element.
 18. A solidphotographing element comprising: a near-infrared cut filter obtainedusing the near-infrared-absorbing composition according to claim
 1. 19.A camera module comprising: a solid photographing element; and anear-infrared cut filter disposed on a light-receiving side of the solidphotographing element, wherein the near-infrared cut filter according toclaim 15 is used.
 20. A process for producing a camera module includinga solid photographing element and a near-infrared cut filter disposed ona light-receiving side of the solid photographing element, comprising:forming a near-infrared cut filter by applying thenear-infrared-absorbing composition according to claim 1 to thelight-receiving side of the solid photographing element.